Reduced calorie triglyceride mixtures

ABSTRACT

Fat mixtures enriched with triglycerides having long, saturated, preferably C 16  to C 22 , fatty acid residues and short, preferably C 2  to C 4 , acid residues are employed in edible compositions as low calorie fats. The preferred embodiments comprise mixtures of at least two triglycerides bearing long residues (e.g. stearyl) and short residues (e.g. acetyl or propyl). In one preferred embodiment, each triglyceride contains short chain residues which are different from those in the other triglyceride. In another preferred embodiment, at least a portion of the triglycerides have two different short residues. Methods of using the low calorie fats and food products incorporating them, particularly in coating, shortening and margarine products, are disclosed.

This is a divisional application of U.S. Ser. No. 08/083,795, filed Jun.28, 1993, now U.S. Pat. No. 5,378,490, which is a divisional applicationof U.S. Ser. No. 07/804,140, filed Dec. 6, 1991, now U.S. Pat. No.5,258,197, which is a continuation-in-part of U.S. Ser. No. 07/624,056,filed Dec. 7, 1990, now abandoned, which is a continuation-in-part ofU.S. Ser. No. 410,161, filed Sep. 20, 1989, now abandoned, and acontinuation-in-part of U.S. Ser. No. 07/665,629, filed Mar. 6, 1991,now abandoned and a continuation-in-part of U.S. Ser. No. 07/732,518,filed Jul. 19, 1991, now abandoned.

TECHNICAL FIELD

This invention relates to the use of low calorie triglyceride mixturesin edible compositions.

Dietary fat is the most concentrated source of energy of all thenutrients, supplying 9 kcal/gram, about double that contributed byeither carbohydrate or protein. The amount of fat in the American diethas increased in the last 60 years by about 25% (Mead, J., etai. Lipids,Plenum, N.Y., 1986, page 459), so that fats now provide approximately40% (or more) of the daily caloric intake.

Fat contributes to the palatability and flavor of food, since most foodflavors are fat-soluble, and to the satiety value, since fatty foodsremain in the stomach for longer periods of time than do foodscontaining protein and carbohydrate. Furthermore, fat is a carrier ofthe fat-soluble vitamins, A, D, E, and K, and the essential fatty acids,which have been shown to be important in growth and in the maintenanceof many body functions. Hence, major research efforts have focused onways to produce food substances that provide the same functional andorganoleptic properties as fats, but not the calories. Synthetic fatshave been created and are now undergoing testing for safety.Unfortunately, many consumers are concerned with the syntheticconnotation of food additives of this type and will not avail themselvesof the advantages they offer.

There is a need for a fat which is low in calories and high infunctionality, but is not perceived as artificial.

BACKGROUND ART

The most abundant group of fats are triglycerides--esters of fatty acidswith glycerol (1,2,3-propanetriol). Natural fats have a broad range offunctionalties and are handled in different ways by the human digestiveprocess.

Early studies reported that triglyceride fats having high melting pointswere less digestible (Deuel, H. J., The Lipids, vol. II, IntersciencePublishers, 1955, pages 218 to 220). Later investigators questioned therelationship between digestibility and melting points, and scrutinizedinstead the chain lengths and degree of unsaturation of fatty acidsubstituents; straight chain, saturated fatty acids having 4 up to 10carbon atoms were completely digested by rats, those having 10 to 18carbons progressively less digested, and those having 18 or higher onlyslightly absorbed, while monounsaturated acids were about the same assaturated acids having 6 carbons (Carroll, K. K., J. Nutr. 64:399-410(1957) at 408).

In other triglyceride metabolic studies in man only limited areas ofpredictability could be found. In one study a coconut oil fractioncontaining predominantly saturated, long chain triglycerides bearing 89%stearic (C₁₈) and 11% palmitic (C₁₆) acid residues were absorbed 31%,compared to 98% for corn oil (Hashim, S. A., and Babayan, V. K., Am. J.Clin. Nutr. 31:S273-276 (1978)). However, it was found that increasingthe stearic acid content of dietary fat did not per se decreaseabsorbability; rather, absorbability could be decreased by increasingthe amount of tristearin present (i.e., triglycerides having threestearic residues; see Mattson, F. H., J. Nutr. 69:338-342 (1959)). Tothis observation were added the findings that, in the presence orabsence of dietary calcium and magnesium, stearic acid was well absorbedby rats when esterified on the 2-position of triglycerides having oleicacid at the 1- and 3-positions, but absorption decreased when a secondstearic was added to the 1-position (Mattson, F., et al., J. Nutr. 109:1682-1687 (1979), Table 3, page 1685). Stearic acid in the 1-positionwas well absorbed from triglycerides having oleic in the 2- and3-positions in the absence, but not in the presence, of dietary calciumand magnesium (ibid.). When stearic was in both the 1- and 3-positions,absorption decreased with or without dietary calcium and magnesium, butthe effect was more pronounced when calcium and magnesium weresufficient (ibid.).

The digestibility of palmitic acid has also been studied. Palmitic acidwas better absorbed by rats when situated at the 2-positions oftriglycerides than at the 1- or 3- positions in naturally occurring fatscommonly fed to infants, and total fat absorption was adverselyinfluenced by increasing the palmitic and stearic acid content in the 1-and 3-positions (Tomerelli, et el., J. Nutr. 95: 583-590 ( 1968)).

While triglycerides high in stearic acid are less well utilized thanothers, they also tend to be high melting. Tristearin is a solid at roomtemperature; the alpha form is a white powder that melts at 55° C.,which, on solidification, reverts to the beta form that melts again at72° C. The melting points of 1,3-distearin with short or medium chainfatty acids at the 2-position are high (Lovegren, N. V., and Gray, M.S., J. Amer. Oil Chem. Soc. 55: 310-316 (1978)). Symmetrical disaturatedtriglycerides of stearic acid and/or palmitic, often with oleic at the2-position, melt fairly uniformly near body temperature, and thisproperty is of advantage for cocoa butter and hard butter substitutes(see, for example, U.S. Pat. No. 4,364,868 to Hargreaves, U.S. Pat. No.4,839,192 to Sagi, et al., and U.S. Pat. No. 4,873,109 to Tanaka, etal.), and for hardstocks for margarines and shortenings (see, forexample, U.S. Pat. No. 4,390,561 to Blair, et al., U.S. Pat. No.4,447,462 to Tafuri and Tao, U.S. Pat. No. 4,486,457 to Schijf, et el.,U.S. Pat. No. 4,865,866 to Moore, and U.S. Pat. No. 4,883,684 to Yang).Because of their functionality, high melting, high stearic fats havelimited applications in food compositions requiring more plastic orliquid triglycerides.

Fats have been prepared by substituting acetic acid for a portion of thefatty acids occurring in ordinary fats or oils, thus producingtriglycerides bearing short acetyl and long substituents. For saturatedfats high in stearic acid, the substitution of acetyl groups for aportion of the stearyl groups lowers the melting point. Theseacetoglycerides were investigated during the 1950's and found to bedigestible. Feeding studies indicated that the nutritive value of mono-and diacetin fats were essentially the same to animals as those fed thecorresponding conventional triglycerides (Mattson, F. H., et al., J.Nutr. 59: 277-285 (1956), although acetooleins were more digestible thanacetostearins (Ambrose, A. M., and Robbins, D. J., J. Nutr. 58:113∝124(1956) and animals grew poorly when fed acetostearin as the sole dietaryfat (Coleman, R. D., et al., J. Amer. Oil Chem. Soc. 40:737-742 (1963)).

While lower melting than tristearin, acetostearins still have highmelting points, limiting applications in food products requiring plasticor liquid fats. In fact, though melting points of compounds structurallyrelated generally decrease with decreasing molecular weight (and mono-and distearins having medium to long saturated substituents follow thisrule), the melting points of triglycerides in the C₁₈ C_(n) C₁₈ andC_(n) C_(n) C₁₈ series, where n=2 to 6, anomalously show the highmolecular weight C₆ (caproic acid) mono- and distearin derivatives tohave the lowest melting points and the low molecular weight C₂ (aceticacid) mono- and distearin derivatives to have the highest (Jackson, F.L., et al., J. Amer. Chem. Soc. 73: 4280-4284 (1951) and Jackson, F. L.,and Lutton, E. S., J. Amer. Chem. Soc. 74:4827-4829 (1952); see also thedata in Example 38). Plastic fats containing acetostearins suggested foruse as shortenings and the like were formulated to contain significantlevels of unsaturated fats and typically employed significant levels offatty acids which would yield high saponification numbers or were liquidat room temperature (U.S. Pat. No. 2,6714,937 to Baur and Lange (1952)and Baur, F. J., J. Amer. Oil Chem. Soc. 31:147-151 (1954)).

Acetostearins are waxy fats having sharp melting points. In contrast tofats bearing medium and/or long substituents, acetostearins also exhibitunusual polymorphism (ibid., and Feuge, R. O., Food Technology 9:314-318 (1955)). Because of their melting and crystal properties, thefats have been suggested as useful for coating food products such asmeat, fish, cheese, and candy (U.S. Pat. No. 2,615,159 to Jackson andU.S. Pat. No. 2,615,160 to Baur). Compositions of this nature are oftenreferred to as "hot melts" and may contain antibiotics (U.S. Pat. No.3,192,057 to Hines and Shirk) or polymeric materials (U.S. Pat. No.3,388,085 to Levkoff and Phillips) to prolong the life of the coating.

The short chain fatty acids, acetic, propionic, and butyric acid, alsocalled, as a group, volatile fatty acids, occur in the large intestineof all mammalian species so far studied (Cummings, J. H., Gut 22:763-779(1981)). Except for a small percentage of butyric acid in milk fat(i.e., about 3.5 to 4%), volatile fatty acids rarely occur in natureesterified to glycerol in fats, but are, instead, generally freeby-products of fermentation in the gut. Physically, short chain fattyacids "are not at all `fatlike` in character; in fact they arehydrophilic substances with complete miscibility with water" (Bailey'sIndustrial Oil and Fat Products, 4th. ed., J. Wiley, N.Y., 1979, volume1, pages 16 to 17).

Early reports investigating the metabolism of short acids andtriglycerides bearing short chain residues showed no regularrelationship between nutritional value and the number of carbon atoms inthe fat (Ozaki, J., Biochem. Z. 177: 156-167 (1926) at 163). Forexample, when fed to rats at levels of 5% and 10% of the diet, triacetinand tributyrin were nutritious, yielding weight gains in the top 20 to25% of the fats tested, whereas tripropionin and triisovalerin weretoxic (ibid.). In 1929, Eckstein reported that rats fed triolein andsodium butyrate grew at the same rate (J. Biol. Chem. 81:163-628 (1929)at 622) .

In 1935, L. E. Holt, et al., observed that infants fed milk enrichedwith tributyrin retained more fat per day (90.1 to 90.2%) than those ina butterfat control group (88.9%); the study concluded that absorptionwas favored by fatty acids with relatively short chains (J. Ped. 6:427-480 (1935), Table VIII, page 445, and Conclusions, number 4, page477). Similar results were obtained with triacetin, with absorption oftributyrin and triacetin reportedly superior to that of corn oil,although corn oil yielded higher calories (Snyderman, S. E., et al.,Arch. Dis. Childhood 30:83-84 (1955)). Substitution of triacetin,tripropionin, or tributyrin for half the glucose and starch in a ratdiet did not significantly affect the digestible, metabolizable or netenergy measurements, but lower body weight gains were observed inanimals fed tributyrin in two experiments and triacetin in oneexperiment (McAtee, J. W., et al., Life Sci. 7:769-775 (1968)).

In in vitro digestibility studies, tributyrin is readily cleaved bypancreatic lipase. Data measuring lipolysis as a function of chainlength show tributyrin much more rapidly hydrolyzed than othersubstrates (see Sobotka, H., and Glick, D., J. Biol. Chem. 105:199-219(1934), comparing triglycerides bearing three identical C₄ to C₁₈ acylgroups, and Desnuelle, P., and Savary, P., J. Lipid Res. 4:369-384(1963), comparing triglycerides bearing three identical C₂ to C₁₈ acylgroups), although some reports rank tripropionin slightly better(Weinstein, S. S., and Wynne, A. M., J. Biol. Chem. 112: 641-649 (1936),comparing triglycerides bearing three identical C₂ to C₆ acyl groups,and Wills, E. D., in Desnuelle, P., ed., The Enzymes of LipidMetabolism, Pergamon Press, N.Y., 1961, pages 13 to 19, comparingtriglycerides bearing three identical C₂ to C₁₈ acyl groups). In fact,because tributyrin is such a good substrate and because the triglycerideis sufficiently water-soluble to allow enzymatic measurements in ahomogeneous solution, it is often selected as a lipase substratestandard (Ravin, H. A., and Seligman, A. M., Arch. Biochem. Biophys.42:337-354 (1953) at 353).

Other lipase preparations readily cleave short chain triglycerides.Tributyrin was found to be hydrolyzed with the greatest initial velocityby human milk lipase, while pig liver lipase hydrolyzed tripropionin andtributyrin with an equal initial velocity much greater than any other ina study comparing C₂ to C₁₈ triglycerides (Schonheyder, F., andVolqvartz, K., Enzymologia 11:178-185 (1943)). Tributyrin was hydrolyzedmore readily than C₆ to C₁₈ triglycerides by human milk bilesalt-activated lipase (Wang, C. S., et al., J. Biol. Chem. 258:9197-9202 (1983)). A liver lipase hydrolyzed trivalerin the fastest,with tributyrin the second fastest (Sobotka and Glick, cited above).

In contrast to triglycerides bearing long chain (˜C₁₆ to C₂₄) fattyacids and those bearing short chain fatty acids, medium chaintriglycerides, generally obtained from kernel oils or lauric fats andencompassing those substituted with C₆ to C₁₂, predominantly C₈ to C₁₀,fatty acids, have been of particular interest because they are morerapidly absorbed and metabolized, via a different catabolic route thanthose bearing long chain fatty acids (see a recent review by Babayan, V.K., in Beare-Rogers, J., ed., Dietary Fat Requirements in Health andDevelopment, A.O.C.S. 1988, chapter 5, pages 73 to 86). Hence, mediumchain triglycerides have been employed in premature infant formulas andin the treatment of several nalabsorption syndromes (ibid.). Feedingstudies by H. Kaunitz, et al., demonstrated the usefulness of mediumchain triglycerides in weight maintentance and obesity control in rats(J. Amer. Oil Chem. Soc. 35:10-13 (1957)).

Several research groups have exploited the physical and nutritionalproperties of medium chain fatty acids by suggesting that triglycerideshaving stearic and/or behenic acid in combination with medium chainsubstituents be used as low calorie fats (Eur. Pat. Ap. Pub. No.322,027, corresponding to U.S. application Ser. No. 132,400, to Seiden,who defined medium chain substituents as comprising C₆ to C₁₀ residues,and Jap. Pat. Pub. No. 2-158,695 to Yoshida, et al., who defined mediumchain substituents as comprising C₄ to C₁₂ residues. The latterpublication, however, exemplified only trace amounts of C₄ fatty acids,and suggested incorporating 0 to 1 long chain, unsaturated residues aswell.) Low calorie triglyceride mixtures having stearic acid at the1-position and medium and unsaturated residues in the other positionshave also been suggested (U.S. Pat. No. 4,832,975 to Yang).

The polymorphism of triglycerides bearing medium and long moietiesgenerally resemble fats bearing long moieties in that they tend to havea stable beta crystal structure. This contributes to graininess of fatmixtures containing them, and, in chocolate compositions, to theappearance of bloom. The preparation of smooth blends require carefulsubstituent selection and/or tempering. It would be desirable to havelow calorie fat mixtures free of this disadvantage. It would also bedesirable to have a fat which was a true triglyceride but whichdelivered a minimum of calories and exhibited functionalities whichpermitted use in a wide variety of products.

Disclosure of the Invention

An object of the present invention is to provide a new group of lowcalorie triglycerides and food compositions incorporating them.

It is a principal object of this invention to provide natural lowcalorie fats.

It is a further object of this invention to provide reduced calorie fatshaving excellent organoleptic properties and functional characteristicsuseful in a wide variety of foods.

These and other objects are accomplished by the present invention, whichprovides mixtures enriched with triglycerides having both long,saturated, preferably C₁₆ to C₂₂, fatty acid residues and short,preferably C₂ to C₄, acid residues. These mixtures are employed inedible compositions as low calorie fats. Most preferably, the long fattyacid residues will be C₁₈ and the short acid residues will be C₂ to C₃.

Denoting the aliphatic portion of the long fatty acid substituent as Land the short as S, the mixtures are enriched with one or more SSL, SLS,LLS, and LSL species described by the following formulae: ##STR1## whereeach R, independently, is a long chain saturated fatty acid residuehaving between 16 and 40 carbons, preferably 18 to 22 carbons; and eachR', independently, is a short chain acid residue having 2 to 5 carbons,preferably 2 to 4 carbons, most preferably 2 to 3 carbons.

Depending upon the preparative procedure (to be more fully describedbelow), the mixtures may also contain triglycerides of the formulae##STR2## where R and R' are as defined above. However, preferredmixtures contain essentially no SSS and preferably less than 2%, morepreferably less than 1%, LLL.

As depicted above, the triglycerides employed in this invention arecompounds consisting of three molecules of the same or different acidsesterified to glycerol, 1,2,3-propanetriol, having the formula (CH₂ OH)₂CHOH. The acids are short C₂ to C₅ acids, or long and saturated C₁₆ toC₄₀ acids.

One preferred embodiment is a mixture of at least two of the abovedescribed triglycerides, at least one bearing two different shortresidues as R' groups. Another preferred embodiment is a mixture of atleast two triglyceride fats each bearing a similar array of long,saturated residues but a different complement of short chain residues.

Methods of using the low calorie fats and food products incorporatingthem are also disclosed. The low calorie triglycerides of this inventionare especially advantageous in coating fat compositions comprising atleast about 75%, preferably at least about 85%, more preferably at leastabout 90%, by weight SSL and SLS species and between about 0.1 and about25%, preferably between about 5 and about 10%, by weight LLS and LSLspecies. In chocolate confections, preferred embodiments are employed inamounts effective to reduce bloom.

The low calorie triglycerides of this invention are also especiallyadvantageous in margarine and shortening fat compositions. Preferredshortening fat embodiments contain at least two triglyceride speciesbearing long, saturated acid residues and propionic acid, butyric acid,mixtures of acetic acid and propionic acid, mixtures of acetic acid andbutyric acid, mixtures of propionic acid and butyric acid or mixtures ofacetic acid, propionic acid, and butyric acid residues. Preferredmargarine fat embodiments are trans-free and contain 1 to 95%,preferably 5 to 75%, low calorie fats and 5 to 95%, preferably 25 to95%, edible oil.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows differential scanning calorimetric (DSC) solid fat indicesof tempered cocoa butter (), quench cooled cocoa butter (), and cocoabutter after several months' storage () at ambient temperature.

FIG. 2 shows DSC solid fat indices of chocolate coating compositionscontaining a low calorie triglyceride mixture obtained byinteresterifying 4.5 moles triacetin with 1 mole hydrogenated canola andthen steam deodorizing, run at zero time (), after 11 days (), and after17 days () at ambient temperature, compared with a control coatingcomposition containing tempered cocoa butter ().

FIG. 3 shows DSC solid fat indices of chocolate coating compositionscontaining a low calorie triglyceride mixture obtained byinteresterifying triacetin, tripropionin, and hydrogenated canola in areactant molar ratio of 2.5:2:1 and then steam deodorizing, run at zerotime () and after 2 days at 25° C. (), compared with a control coatingcomposition containing tempered cocoa butter ().

FIG. 4 shows DSC solid fat indices of chocolate coating compositionscontaining a low calorie triglyceride mixture obtained byinteresterifying triacetin, tripropionin, and hydrogenated canola in areactant molar ratio of 11:1:1 and then steam deodorizing () comparedwith a control coating composition containing tempered cocoa butter ();the melting profile of the low calorie mixture retains a lower thancocoa butter profile for at least 3 months when stored at either 65° F.or 75° F.

FIG. 5 shows DSC solid fat indices of six triglyceride compositions: anall purpose vegetable shortening control () and five low calorietriglyceride mixtures obtained by interesterifying and steam deodorizingtriacetin, tripropionin, and hydrogenated canola in a reactant molarratio of 1:11:1 (), 3:9:1 (), 6:6:1 (), 9:3:1 (), and 11:1:1 ().

FIG. 6 shows a pictorial comparison of cross-sectional geometricalchanges that occur during the baking of otherwise identical cookiescontaining an all purpose vegetable shortening control (left) and a lowcalorie triglyceride test mixture containing 35% diacetyl stearin and65% dipropionyl stearin (right).

FIG. 7 shows DSC solid fat indices of seven triglyceride compositions:an all purpose vegetable shortening control (), a 1:2 blend of diacetylstearin and dibutyryl stearin (), a 1:1 blend of diacetyl stearin anddibutyryl stearin (), a 2:1 blend of diacetyl stearin and dibutyrylstearin (), a 1:2 blend of diacetyl stearin and dipropionyl stearin (),a 1:1 blend of diacetyl stearin and dipropionyl stearin (), and a 4:1blend of diacetyl stearin and dipropionyl stearin ().

General Description of the Invention

Before describing the most preferred aspects of the invention,applicants present the following description of the technology,describing in detail the nature of the compositions of the invention,and how to make and use them.

In the practice of this invention, low calorie food products areformulated with mixtures of triglycerides enriched with short (C₂ to C₄,particularly C₂ to C₃) acid residues and long (C₁₆ to C₂₂) fatty acidresidues.

The short (volatile) acid residue, R', has no more than 5 carbons, morenarrowly 2 to 4, particularly 2 or 3 carbons. R' is derived from acarboxylic acid of the formula SCOOH, where S is a short chain groupsuch as an aliphatic or an hydroxyalkyl having 1 to 4 carbons. Asdenoted herein, where R' is described as having 2, 3, 4, or 5 carbons,compositions with R' groups having predominantly 2, 3, 4, or 5 carbonsare included. Acylation of a glycerol hydroxyl by acid SCOOH results inthe attachment of short chain S to the glycerol backbone by means of anester linkage (--O--(CO)--). Where there is more than one R' attached toa glyceride, the R' groups may be the same or different. As used herein,the term "acid residue" refers to an acyl group comprising a short chainportion, here S, and a carbonyl group, so that R'=S--(CO)--.

Short chain S may be either saturated or unsaturated, straight orbranched. Short chain S may be derived from any synthetic or naturalorganic acid including, but not limited to acetic (ethanoic), propionic(propanoic), butyric (butanoic), valeric (pentanoic), glycolic(hydroxyacetic), lactic (2-hydroxypropanoic), hydracrylic(3-hydroxypropanoic), hydroxybutyric, hydroxypentanoic, and the likeacids. As used herein, chemical names include isomeric variations; forexample, "butyric acid" includes normal-butyric acid (butanoic) andiso-butyric (2-methylpropanoic) acid, "valeric acid" includesnormal-valeric (pentanoic) and iso-valeric (3-methylbutanoic), and soforth. Preferred acids are acetic, propionic, and butyric acids andmixtures of these. Acetic and propionic acids are especially preferred.

Mixtures of acids may also be used, such as, for example, those derivedfrom specific fractions of unhydrogenated, partially hydrogenated orfully hydrogenated dairy butterfat, coconut, palm kernel and the likeoils. For example, butter fat has been fractionated, yielding a fractionenriched with triglycerides having 2 residues of at least 16 carbons and1 residue with 2 to 8 carbons (though the Examples illustrated only 4 to8 carbons for the shorter moiety, U.S. Pat. No. 4,479,097 to Lansbergenand Kemps, column 5, Tables 2 and 4, and U.S. Pat. No. 4,504,503 toBiernoth and Merk, column 3, Tables 1 and 2); the butterfat stearinefraction was said to improve the butter-like properties of margarine.

The low calorie triglycerides of this invention generally contain 33 to67 mole % short acid residues. Fatty acid mixtures can contain amountsof medium or long, unsaturated fatty acids to the extent which these canbe tolerated without unduly affecting the physical properties of thefat, or the caloric reduction. For example, some products may contain upto 20% medium and/or long, unsaturated triglycerides.

The long fatty acid residue, R, has from 16 to 40 carbons, more narrowly16 to 24, more narrowly, 18 to 22, and even more narrowly 18 to 20carbons. In one embodiment, R has predominantly (≧70 to 80%, or higher)18 carbons (stearic acid residues). In another embodiment R has ≧90% C₁₈(stearic acid residue) R groups. R is an acyl group comprising analiphatic portion and a carbonyl, and is derived from a fatty acid ofthe formula LCOOH, where L is a saturated aliphatic group having 15 to39 carbons; thus, R=L--(CO)--. Acylation of a glycerol hydroxyl by acidLCOOH results in the attachment of long chain L to the glycerol backboneby means of an ester linkage (--O--(CO)--). Where there is more than oneR group attached to a glycerol backbone, the R groups may be the same ordifferent.

R may be derived from any synthetic or natural, straight or branchedsaturated organic acid including, but not limited to, palmitic(hexadecanoic), stearic (octadecanoic), arachidic (eicosanoic), behenic(docosanoic), lignoceric (tetracosaenoic), cerotic (hexacosanoic),montanic (octacosanoic), melissic (triacontanoic), and the like acids. Rmay also be derived by hydrogenating an unsaturated acid including, butnot limited to, palmitoleic (9-hexadecenoic), oleic(cis-9-octadecenoic), elaidic (trans-9-octadecenoic), vaccenic(trans-11-octadecenoic), linoleic (cis, cis-9,12-octadecedienoic),linolenic (9,12,15-octadecatrienoic and 6,9,12-octadecatrienoic),eleostearic (9,11,13-octadecatrienoic), arachidonic(5,8,11,14-eicosatetraenoic), nervonic (cis-15-tetracosenoic),eicosapentaenoic, docosatetraenoic, docosapentaenoic, docosahexaenoic,and the like acids. Chemical names include isomeric variations.

The various R groups can be mixtures of fatty acids and can be derived,for example, from non-hydrogenated, partially hydrogenated or fullyhydrogenated oils such as soybean, safflower, sunflower, high oleicsunflower, sesame, peanut, corn, olive, rice bran, babassu nut, palm,mustard seed, cottonseed, poppyseed, low erucic rapeseed, high erucicrapeseed, shea, marine, meadowfoam and the like oils. Preferred oils arehydrogenated, preferably fully hydrogenated. Hydrogenated fats having atleast about 70%, preferably at least about 75%, stearic acid residuessuch as hydrogenated peanut oil, hydrogenated olive oil, hydrogenatedsoybean oil, hydrogenated sesame oil, and hydrogenated corn oil areespecially desirable for some embodiments. Other embodiments employhydrogenated fats having at least about 90% stearic acid residues, suchas hydrogenated sunflower oil, hydrogenated safflower oil andhydrogenated canola. Fatty acids derived from processed or unprocessedtallow, lard, shea butter, and dairy butter, or plant waxes such asjojoba may also be used. Specific fractions of processed or unprocessedoils, fats, or waxes may be used, and are especially advantageous insome embodiments.

The oils, fats, or waxes may be hydrogenated before or afterincorporation into the low calorie triglycerides of this invention. Themixtures can contain amounts of medium or unsaturated long fatty acidsto the extent which these can be tolerated without unduly affecting thephysical properties of the fat, or the caloric reduction. For example,some products may contain up to 20% medium and/or unsaturated long fattyacids. The caloric reduction is best taken advantage of when the levelof these acids is maintained at less than 15%, more desirably less than10%.

Some of the compounds of this invention may be described by the formula##STR3## where

x, y, and z=n or m n=0, 1, 2, or 3, m=16, 18, 20 or 22, and14≦(x+y+z)≦47.

The long and short substituents are selected to provide a discerniblefatty character in the mixtures. An advantage of the present inventionis that functional properties can be modulated by the selection of S andL groups as well as by the proportions of SSS, SLS, SSL, LLS, LSL andLLL components in the mixtures. Formulations for chocolate orconfectionery applications, for example, can employ groups or componentsyielding high, sharply melting mixtures, salad oils can employ groups orcomponents yielding medium melting mixtures that do not readilycrystallize upon refrigeration, margarines and shortenings can employgroups or components yielding plastic mixtures, bakery products mayemploy groups or components stable to oxidation on storage, and soforth. Particular formulations are set forth hereinafter.

The molar ratio of S to L groups in the SSS, SLS, SSL, LLS, LSL and LLLlow calorie mixtures of this invention may be determined using proton orcarbon nuclear magnetic resonance (hereinafter referred to as NMR), orany quantitative procedure known to those skilled in the art. The S/Lratio generally varies between 0.5 and 2.0. Using this parameter, manyof the mixtures of this invention fall into one of three major groups:the first has an S/L ratio of 0.5 to 1.0; the second, 1.0 to 1.5; andthe third, 1.5 to 2.0.

In some embodiments, mixtures having higher capillary melting points,e.g., melting above 50° C., preferred for certain food applications,fall into the first group and have S/L ratios that vary between 0.5 and1.0. Some mixtures having mid-range melting points, e.g., meltingbetween ˜25° to 30° and 50° C., preferred for other applications, fallinto the second group and have S/L ratios that vary between 1.0 and 1.5.Some mixtures having lower melting points, e.g., melting below 25° C.,fall into the third group and have S/L ratios that vary between 1.5 and2.0. Specific examples are set forth hereinafter.

In one embodiment, the triglyceride mixtures of this invention havecapillary melting points from 10° to 25° C. Another melts at 20° to 30°C. Another embodiment melts at 33° to 39° C. Others melt above 40° C.,with one embodiment having a capillary melting point of 50° to 60° C. Anadvantage of the present invention is that the melting point ranges canbe tailored by the choice of the short and long acid residues and theamount of SSL/SLS and SLL/LSL in the mixtures. Mixtures can be furthervaried by adding SSS or LLL species, or conventional triglycerides.

Moreover, the choice of the short and long acid residues and the amountof SSL/SLS, SLL/LSL, SSS, LLL and conventional fats in the mixtures canbe used to modulate the solids contents for fats having the same (ordifferent) capillary melting points so that the functional propertiesmay be further modified. By the term "solids content" is meant thepercentage of a fat that exists in crystalline form at a giventemperature. Solid fat contents (herein abbreviated S.F.C.) aredetermined using nuclear magnetic resonance according to A.O.C.S. MethodCd 16-81. Unless otherwise indicated, solid fat indices (hereinabbreviated S.F.I.) are determined using dilatometry according toA.O.C.S. Method Cd 10-57. Solids percentages are reported at 50° F. (10°C.), 70° F. (21.1° C.), 80° F. (26.7° C.), 92° F. (33.3° C.), and 100°F. (37.8° C.). Example S/L ratios, melting points, S.F.C.'s, andS.F.I.'s are given hereinafter.

The molar percentage of LLS and LSL in the mixtures can range from 0 tonearly 100%. In some embodiments, the LLS and LSL molar percentage isless than about 25%, preferably less than 15%, and even more preferablyless than 5%. In others, the molar percentage is higher, ranging between25 and 40%. One preferred embodiment is 15 to nearly 20 mole percentLLS/LSL; another is 20 to nearly 25%; another is 25 to 30%.

The molar percentage of SLS and LSS in the mixtures can range between 0to nearly 100%, more narrowly 10 and 90%, even more narrowly 15 to 85%.In some embodiments, the LSS/SLS molar percentage ranges between 75 and100%; in others, between 85 and 100%. One preferred embodiment is 40 tonearly 60 mole percent LSS/SLS; another is 60 to nearly 70%; another is90 to 100%. One especially preferred embodiment has greater than 80%,preferably greater than 85%, even more preferably greater than 97% SSLand SLS. It is advantage of the invention that low calorie fatscontaining large amounts of LSS/SLS have small amounts of L moieties.

The molar percentage of LLL in the mixtures is generally under 10%, morenarrowly less than 5%. In some embodiments, mixtures having less than 3%LLL are preferred. In others, less than 1% is preferred. The molarpercentage of SSS in the mixtures is generally under 10%; preferredmixtures contain less than 5% SSS, more narrowly less than 3%; manyembodiments contain essentially no SSS species.

Based on relative proportions of S and L substituents, the low calorietriglyceride mixtures of this invention can be placed into three majorgroups:

Group I comprises mixtures wherein the molar ratio of short to long(S/L) substituents falls between 0.5 and 1.0. These mixtures tend tohave higher capillary melting points; many embodiments melt above 50°C., and thus are solids at room temperature.

Group II comprises mixtures wherein the molar ratio of short to long(S/L) substituents varies between 1.0 and 1.5. These mixtures tend tohave mid-range melting points; many embodiments melt between ˜25° and˜50° C.

Group III comprises mixtures wherein the short to long (S/L) molar ratiovaries between 1.5 and 2.0. These mixtures tend to have lower meltingpoints. Some embodiments melt below 25° C., and are fluids at roomtemperature.

One embodiment of this invention comprises a triglyceride mixture of:##STR4## Preferred mixtures of this type contain a mixture of at leasttwo R' groups and more SSL than SLS. Many of the compounds of this typemay be described by the formula ##STR5## where

x, y, and z=n or m n=0, 1, 2, or 3 m=16, 18, 20 or 22, and14≧(x+y+z)≧28.

One especially preferred embodiment has x+y+z=17.

Another embodiment of this invention comprises a triglyceride mixtureof: ##STR6## These generally have higher melting points than mixtures ofSSL and SLS, especially where the LSL species predominates. Somepreferred mixtures contain a mixture of two or more R groups, such asfor example, R groups derived from cottonseed, soybean or fish oils;some of these contain a mixture of two or more R' groups, such as, forexample a mixture of R' groups derived from acetic and propionic acid.

Many of the LLS/LSL mixtures can be described by the formula ##STR7##where

x, y, and z=n or m n=0, 1, 2, or 3, m=16, 18, 20 or 22, and29≧(x+y+z)≧46.

Component triglycerides making up the low calorie fat mixtures of thisinvention may be prepared using synthetic procedures known to thoseskilled in the art, such as, for example, directly esterifying glycerolor glycerol esters with fatty acids, fatty acid halides (notablychlorides) or fatty acid anhydrides, transesterifying glycerol withfatty acid esters, or interesterifying long and short chaintriglycerides for such time and under such conditions that triglyceridesbearing long and short residues form. Starting materials fortriglyceride preparations may be obtained commercially or isolated fromnatural sources. Alternatively, component triglycerides may be isolatedfrom natural or processed fats or oils, or fractions thererof, asdiscussed above. Examples prepared are set out in the next section.

Some desirable triglyceride mixtures are prepared using a randominteresterification of triacetin, tripropionin and/or tributyrin with asubstantially hydrogenated fat having at least about 70%, in some casesat least about 75%, more preferably at least about 90%, stearic acidresidues. An advantage of this invention is that the preparativeprocedure for many mixtures can be facilitated by employing at least twotriglycerides bearing only short triglycerides. For example, because ofsolubility differences, triacetin reacts sluggishly with hydrogenatedcanola, but in the presence of tripropionin, the reaction isfacilitated.

Some preparative procedures for triglycerides bearing short and longsubstituents have been published. Interesterification of a shorteningbasestock with triacetin yielded an improved plastic product (though allthe Examples employed partially, not fully, hydrogenated basestocks; seeU.S. Pat. No. 2,614,937 to Baur and Lange). Acetylated monoglycerideshave been discussed above. An acetylated monoglyceride prepared fromlard, cottonseed oil or partially hydrogenated vegetable oil has beendisclosed as useful in lowering cholesterol (U.S. Pat. No. 4,272,548 toGatzen, et al.). Triglycerides bearing palmitic and butyric residueswere synthesized for study as pancreatic lipase and human milk bilelipase substrates (in Clement, G., et al., Biochem. Biophys. Res.Commun. 8:238-242 (1962) and Wang, C. S., et al., cited previously,respectively).

The low calorie triglycerides of this invention may be incorporatedeither alone, or in combination with another fat and/or fat mimetic,into any food composition, or used in conjunction with any ediblematerial. Other fats include natural triglycerides rich in highlydesirable or essential fatty acids, such as oleic, linoleic, linolenic,or eicosapentaenoic acid, triglycerides bearing fatty acids havingbeneficial attributes such as those associated with conjugated linoleicacid isomers, medium chain triglycerides and the like. Other fatmimetics include any heretofore suggested as edible fat replacements,including, but not limited to, sugar esters, neoalkyl esters,polyglycerol esters, malonate esters, propoxylated glycerols, retrofats,carboxy/carboxylates, polyvinyl alcohol esters and the like. Whenemployed either alone or in products with other fats, they are desirablyadded in amounts effective to provide a significant caloric reduction ofthe calories due to fat. For example, a 10% or greater replacement wouldbe effective for this purpose, and replacements of at least 25%, moreparticularly 50 to 100%, are desired in many cases.

The term "edible material" is broad and includes anything edible,whether or not intended for nutrition, e.g., it can be an additive suchas an antioxidant for fats or oils, an antispatter agent, an emulsifier,a texture modifier such as a plasticizer for chewing gum, a componentfor cosmetics, or other minor functional ingredient such as a carrier ordiluent for use in flavorings, pharmaceuticals, and the like.

Broadly speaking, the reduced calorie triglycerides of this inventioncan be employed as fat replacements in fat-containing edible emulsionscomprising an oil phase and an aqueous phase, including those high infat, such as margarines and salad dressings, and those high in water,such as low fat spreads. The triglycerides of this invention can beemployed as full or partial fat substitutes in dairy, meat, nut, egg,and other food products having a high natural fat component, and invegetable, cereal and other products having a low natural fat component.The triglycerides of this invention can be employed as ingredients forall types of leavened baked products, both yeast raised and chemicallyleavened, and unleavened baked products, and as coatings or coatingingredients for the same types of products. The triglycerides of thisinvention can be employed as an ingredient or a coating for snack foodproducts, as well as a frying oil or a frying oil ingredient for friedsnacks. In addition, the low calorie triglycerides of the presentinvention can be employed to form edible barrier layers, either on theexposed surfaces of foods or as internal barrier layers used to separatevarious portions of a food product, e.g., in frozen pizza, nut coatings,or as a barrier between a dessert filling and an outer edible shell infruit filled cookies and the like.

Representative of fat-containing food products which can contain, inaddition to other food ingredients, the low calorie triglycerides ofthis invention in full or partial replacement of natural or syntheticfat are: frozen desserts, e.g., frozen novelties, ice cream, sherbet,ices, and milk shakes; salad dressings; mayonnaises and mustards; dairyand non-dairy cheese spreads; margarine, margarine substitutes andblends; flavored dips; flavored bread or biscuit spreads; filled dairyproducts such as filled cream and filled milk; frying fats and oils;cocoa butter replacements and blends; candy, especially fatty candiessuch as those containing peanut butter or chocolate (to which antibloomproperties may be imparted); reformed and comminuted meats; meatsubstitutes and extenders; egg products and substitutes; nut productssuch as peanut butter; vegetable and fruit products; pet foods; whippedtoppings; compound coatings; coffee lighteners, liquid and dried;puddings and pie fillings; frostings and fillings; chewing gum;breakfast cereals; bakery products, e.g., cakes, breads, rolls,pastries, cookies, biscuits, and savory crackers; and mixes oringredient premixes for any of these. The low calorie triglycerides ofthis invention may also be employed in any flavor, nutrient, drug orfunctional additive delivery system.

An advantage of the present invention is that the low calorietriglycerides of this invention may be mixed with natural oils so thatthe ratio of unsaturated to saturated residues in certain food productssuch as margarine is greater than 2.5. In one embodiment, thepolyunsaturated to saturated ratio lies between 1 and 2; in another, theratio is greater than 2.

The following is a list of representative, but not limiting,triglycerides which may be employed in the mixtures of this invention:##STR8## Other example structures and compounds are set out in the nextsection, with further particulars as to syntheses and/or physicalproperties. Also illustrated in the next ection are mixtures derivedfrom natural oils. Other nonlimiting examples of component triglyceridesso derived include compounds of the formula:

Acetylated Hydrogenated Soybean Oil Derivatives ##STR9## where the Rgroups are derived from hydrogenated soybean oil

Low Calorie Hydrogenated High Oleic Sunflower Oil Derivatives ##STR10##where R' is a mixture of --(CO)--CH₃ and --(CO)--(CH₂)₂ CH₃ and the Rgroups are derived from hydrogenated high oleic sunflower oil.

Acetylated/Propionylated Hydrogenated Shea Oil Derivatives ##STR11##where R' is a mixture of --(CO)--CH₃ and --(CO)--CH₂ CH₃, and the Rgroups are derived from hydrogenated shea oil and the like.

Description of Preferred Embodiments

This invention is based upon surprising findings that short chain acidsother than acetic or in addition to acetic can be employed to improvethe functional properties of acetostearins. In some cases, theproperties can be drastically changed simply by mixing the acetylresidues with one or more other volatile acid residues, by substitutingone or more volatile acid residues for acetyl residues, or by admixingacetostearins with one or more structurally similar fats that havedifferent short substituents, even though the similar fat, by itself,more closely resembles pure acetostearins than it does the mixture.

Moreover, certain combinations of triglycerides bearing short andsaturated, long triglycerides, especially mixtures that contain anenriched amount of at least two short chain acids, are low in caloriesand have an array of desirable characteristics in food applications,including oxidative stability, smooth organoleptic properties, uniquesolids profiles, and resistance to bloom. Food products employing thesedesirable triglycerides also exhibit moisture retention andinterestering baking characteristics.

In one preferred embodiment, the low calorie triglycerides of thisinvention bear mixtures of at least two short chain acid residues.Preferred mixtures are acetic and propionic acid residues, acetic andbutyric acid residues, propionic and butyric acid residues, and acetic,propionic, and butyric acid residues.

In another preferred embodiment, the low calorie triglycerides aremixtures of at least two triglycerides bearing long, saturated residuesbut different complements of short chain groups. Thus, mixtures of atleast two triglycerides bearing acetic acid residues or propionic acidresidues or butyric acid residues or a mixture of acetic acid andpropionic acid residues, or a mixture of acetic acid and butyric acidresidues, or a mixture of propionic acid residues and butyric acidresidues, or a mixture of acetic acid, propionic acid, and butyric acidresidues with long, saturated residues are encompassed. Preferredcombinations of this type are mixtures containing at least twotriglycerides, each bearing acetic, propionic or butyric acid residuesand long, saturated residues.

Candy coating Fats

The low calorie triglycerides of this invention are especiallyadvantageous in coating compositions, especially coatings for candiesand bakery and dessert products. A preferred embodiment comprises amixture of at least two triglycerides of the formulae ##STR12## whereineach R, independently, is a long chain saturated fatty acid residuehaving between 18 and 22 carbons, each R', independently, is a shortchain acid residue having 2 to 4 carbons derived from acetic acid,propionic acid, and/or butyric acid, comprising at least about 75%,preferably at least about 85%, more preferably at least about 90%, byweight SSL and SLS species and between about 0.1 and about 25%,preferably between about 2 and about 10%, by weight LLS and LSL species.

One especially preferred embodiment has R' groups comprising a mixtureof acetic and propionic acid residues. The composition contains about 10to about 25, preferably about 15 to about 25, particularly about 23,weight percent acetic acid residues and about 0.1 to about 10,preferably about 0.5 to about 5, particularly about 4, weight percentpropionic acid residues. As has been described above, these desirablecoatings can be prepared by blending diacetin and dipropionin saturatedfats or by interesterifying triacetin, tripropionin, and a fat enrichedwith long saturated residues such as hydrogenated canola, hydrogenatedsoybean oil or tristearin.

For example, an especially desirable coating fat is prepared by randomlyinteresterifying, using a reactant molar ratio of 11:1:1, triacetin,tripropionin and hydrogenated canola and then steam deodorizing.Chocolate coatings formulated using the triglyceride mixture so obtainedhave a melting profile striking similar to coatings containing cocoabutter (see, for example, FIG. 4), but are low in calories and bloomresistant (an advantage more fully discussed hereinafter).

Other desirable coating fats contain, as short chain substituents, amixture of acetic acid and butyric acid residues, a mixture of propionicand butyric acid residues, or a mixture of acetic, propionic, andbutyric acid residues. A typical coating fat has a melting point ofabout 32° to about 38° C., a solids content of at least about 50% atabout 10° C., and a solids content of less than about 5% at about 30° C.

An advantage of this invention is that preferred chocolate-like coatingfat compositions can be employed in amounts effective to reduce bloom,i.e., in amounts that reduce visually apparent bloom at least about 35%preferably at least about 50%. As is familiar to the skilled artisan,"bloom" is a separation of fat crystals from the matrix of a chocolatecoating, generally caused by separation of cocoa butter from the matrixand extrusion or recrystallization of fat to or on the surface withconsequent white layer or splotches. Bloom is usually ascribed topartial liquefication (due, for instance, to temperature fluctuations)and then recrystallization of the fat which sometimes migrates to thesurface. Although tempering, the formation of stable crystals via acommonly used cooling and slow heating process, can help in retardingbloom, bloom remains a recurring problem in the chocolate confectionindustry. Preferred coating fat embodiments of this invention reducevisually apparent bloom by at least about 90% over two or threetemperature (warming and cooling) cycles and have a unique crystalstructure that requires no tempering. In fact, some can be quenchcooled.

Surprisingly, it has been found that a number of the low calorie fats ofthis invention, when employed in chocolate-type confectionery products,inhibit the formation of visually apparent bloom. For example, when theacetyl/propionyl stearin mixtures disclosed above are used as the fatsubstitute in chocolate-like confectionery compositions, the incidenceof visually apparent bloom is greatly delayed. It is a further advantageof the present invention that the tempering step in the manufacture ofthe confections can be eliminated when the preferred fats are employed.Moreover, especially preferred confection embodiments can withstandfluctuations in temperature that usually give rise to bloom in chocolateconfections even when the chocolate blend has been quench cooled duringmanufacture. The onset of visually apparent bloom can be delayed for atleast about a month, preferably for at least about 6 months, orprevented.

Another advantage of the present invention is that preferred coatingfats are compatible with cocoa butter in all proportions. Thus,confections employing the low calorie triglycerides in partialreplacement of cocoa butter is greatly facilitated. For example, coatingfats of this invention can replace at least about 60% or more of thenatural confectionery fat ingredient such as cocoa butter, which canmake up at least about 35% of the chocolate. A typical chocolateconfectionery composition, for example, contains about 5% to about 40%by weight chocolate flavoring (including chocolate liquor or cocoa whichcontain some inherent fat), about 25% to about 40% by weight fatingredients, and about 0.001% to 40% by weight sweetener.

One preferred coating fat of the invention comprises at least 95%triglycerides bearing one long chain fatty acid residue derived from afat containing at least 90% 18 carbon or higher fatty acid residueshydrogenated to an I.V. value of 3 or less and two short chain residues,each selected from the group consisting of acetic and propionic acidresidues in a molar ratio of 51 to 13, said fat being essentiallytrans-free using A.O.C.S. Method Cd 14-61 and beta crystal free andhaving the following physical properties:

a Mettler Drop point of about 95° F. using A.O.C.S. Method Cc 18-80;

a smoke point of about 260° F. using A.O.C.S. Method Cc 9a-48;

a flash point of about 470° F. using A.O.C.S. Method 9a-48;

a fire point of about 495° F. using A.O.C.S. Method 91-48;

a congeal point of about 33.8° C. using A.O.C.S. Method Ca 14-59;

a specific gravity at 60° C. of about 0.9337 using A.O.C.S. Method Cc10b-25;

a peroxide value of about 0.45 meq/kg using A.O.C.S. Method 8-53;

a refractive index at 60° C. of about 1.4385 using A.O.C.S. Method Cc7-25;

a saponification value of about 347 using A.O.C.S. Method 3-25;

an oxidation stability using A.O.C.S. Method Cd 12-57 for at least 290hours;

a free fatty acid value of about 0.78% using A.O.C.S. Method 5a-40;

an S.F.C. of about 82.1% at 50° F., about 78.4% at 70° F., about 71.7%at 80° F., about 29.9% at 92° F., and about 4.9% at 100° F. usingA.O.C.S. Method Cd 16-81;

a viscosity of about 35.1 cps at 100° F. and about 19.7 cps at 150° F.;

a heat of fusion of about 99.4 mJ/mg;

A Lovibond Color of about 20Red/77Yellow using a 1 inch column followingA.O.C.S. Method Cc 13b-45;

resistance to bloom visually apparent to an analyst trained inidentifying and evaluating bloom; and

essentially no crystals exceeding 8 u observed on microscopicexamination under polarized light.

Margarine Fats

The low calorie triglycerides of this invention are also especiallyadvantageous in margarine fat compositions. Preferred margarine fatembodiments contain at least two triglyceride species bearing long,saturated acid residues and propionic acid, butyric acid, mixtures ofacetic acid and propionic acid, mixtures of acetic acid and butyricacid, mixtures of propionic acid and butyric acid or mixtures of aceticacid, propionic acid, and butyric acid residues. Triglyceride mixtureshaving at least two different long chain moieties are especiallypreferred for some embodiments, such as, for example, long chainresidues obtained from hydrogenated cottonseed or hydrogenated fishoils.

Advantageously, the margarine fats which are either mixtures ofindividual esters, each containing a distinct short acid species, ormixed esters where at least some of the triglycerides contain twodifference short acid residues in addition to a long acid, have lowersaponification values than corresponding acetylated triglycerides ofsimilar melting point. It is a practical advantage that lower meltingpoints and broader melting ranges can be achieved, preferably withdecreased graininess, than for acetylated triglycerides. The techniquesemployed in the art, namely employing some degree of unsaturation,shorter long chain fatty acids (e.g., 14 to 16 carbons), medium chainfatty acids (e.g., 8 to 12 carbons), or higher levels of acetic acid,can still be employed is desired; however, these techniques can bedispensed with by the invention. A further and related advantage appearsfrom the ability, as compared to acetylated triglycerides, to obtain afully saturated oil blend having less C₁₆ and C₁₄ fatty acids. Thus,trans oleic acid-free margarines can be obtained which also havedecreased levels of palmitic and lauric acids. This permits a higherrelative proportion of stearic or higher acid and thus enhances theability to produce a low-calorie product.

The fat mixtures are prepared to yield desirable S.F.I. values. Forexample, SFI values required for an oil phase to be used in a stickmargarine are a minimum solids content of about 15% at 50° F., a minimumsolids content of about 7% at 70° F., and a maximum solids content ofabout 5% at 92° F. Preferably, the maximum solids content at 92° F. willbe less than 4%, most preferably between 1 1/2 to 3 1/2% at 92° F. Atthis specification, the margarine may be formed and wrappedsatisfactorily, maintaining the stick form without substantial oilseparation at room temperature and yet remains rapid melting on thetongue at about 98° F. A more preferred SFI profile will show solidcontents within the following ranges:

    ______________________________________                                        Temperatures   Solids (%)                                                     ______________________________________                                        50° F.   16 to 31                                                      70° F.   11 to 18                                                      92° F.   3.5 maximum                                                   ______________________________________                                    

Desirably, the stick margarine should remain firm at ordinary roomtemperature up to about 80° F., and will therefore most preferably havean SFI value at this temperature within the range of from about 6 toabout 10.

The SFI solids values required for an oil phase to be used informulating a tub margarine are a minimum solids content of about 8% at50° F., and a minimum solids content of about 3% at 70° F. and a maximumsolids content of about 4% at 92° F. Preferably, the SFI profile showssolids contents in the following ranges:

    ______________________________________                                        Temperatures   Solids (%)                                                     ______________________________________                                        50° F.  9 to 15                                                        70° F.  5 to 10                                                        92° F.  3.5 maximum                                                    ______________________________________                                    

One embodiment employs a ratio of low calorie triglycerides to edibleoil between 20:80 and 30:70. An example composition comprises corn oiland one or more low calorie triglycerides selected from the groupconsisting of dibutyryl stearin and butyryl distearin. Other examplesare set forth herinafter.

In the practice of formulating margarines according to this embodiment,effective amounts of low calorie triglycerides are mixed with edibleoils to yield structured lipid compositions. By the term "edible oil" ismeant any natural or synthetic lipid, or mixtures of such lipids, whichflow at 20° C. and are suitable for use in human foods. Preferred edibleoils are liquid at 20° C., with many embodiments liquid at 25° C.Preferred margarine fat compositions contain 1 to 95%, preferably 5 to75%, low calorie fats and 5 to 95%, preferably 25 to 95% edible oil

Edible oils, which are predominantly liquid at 20° C., includesemi-liquid oils that contain significant solid fat which can increasetheir viscosities. Edible oils include vegetable oils such as soybean,safflower, sunflower, high oleic sunflower, sesame, peanut, corn, olive,rice bran, canola, palm, cottonseed, rapeseed, high erucic rapeseed,carrot, evening primrose, borage, and meadowfoam oils. Edible oils alsoinclude animal oils such as marine oils, lard, tallow, and dairy butter.Specific fractions of edible oils may be employed. Mixtures of oilsand/or fractions may be used.

An advantage of the invention is that the margarines prepared using thelow calorie triglycerides of this invention can be formulated so theresulting compositions are trans-free. Most natural fats and oilscontain only cis double bonds, but partial hydrogenation results in theformation of trans fatty acids, which have been recently shown to raiselow density lipoprotein serum cholesterol levels and to lower highdensity lipoprotein serum cholesterol levels in adults fed fats havingthese acids (Mensink, R. P., and Katan, M. B., New Eng. Jour. Med.,323:439-445 (1990)). Since this invention employs natural oils and fullyhydrogenated oils, these isomers can be eliminated from the foodproducts.

One preferred margarine fat of the invention comprises an edible oil andat least 95% triglycerides bearing a mixture of long chain fatty acidresidues derived from a fat containing at least 90% 18 carbon or higherfatty acid residues hydrogenated to an I.V. value of 3 or less andbutyric acid in a molar ratio of about 46 to 54, said triglyceridesbeing essentially trans-free using A.O.C.S. Method Cd 14-61 and betacrystal free and having the following physical properties:

a Mettler Drop point of about 87.6° F. using A.O.C.S. Method Cc 18-80;

a smoke point of about 310° F. using A.O.C.S. Method Cc 9a-48;

a flash point of about 480 ° F. using A.O.C.S. Method 9a-48;

a fire point of about 510° F. using A.O.C.S. Method 91-48;

a congeal point of about 30.6° C. using A.O.C.S. Method Ca 14-59;

a specific gravity at 60° C. of about 0.9097 using A.O.C.S. Method Cc10b-25;

a peroxide value of about 0.20 meq/kg using A.O.C.S. Method 8-53;

a refractive index at 60° C. of about 1.4396 using A.O.C.S. Method Cc7-25;

a saponification value of about 287 using A.O.C.S. Method 3-25;

an oxidation stability using A.O.C.S. Method Cd 12-57 for at least 295hours;

a free fatty acid value of about 0.23% using A.O.C.S. Method 5a-40;

an S.F.C. of about 78.2% at 50° F., about 49.3% at 70° F., about 11.8%at 80° F., about 7.3% at 92° F., and about 7.8% at 100° F. usingA.O.C.S. Method Cd 16-81;

a viscosity of about 32.9 cps at 100° F. and about 26.3 cps at 150° F.;

a heat of fusion of about 121.6 mJ/mg;

A Lovibond Color of about 8Red/79Yellow using a 1 inch column followingA.O.C.S. Method Cc 13b-45; and

essentially no crystals exceeding 8 u observed on microscopicexamination under polarized light.

Low calorie triglycerides of this invention can also be advantageouslyemployed in low fat spread and margarine products. Low, i.e., 20 to 60%,fat spreads can be prepared by emulsifying the fats of this inventionwith an aqueous phase. Preferred fat compositions for low fat spreadshave an array of triglycerides bearing different chain lengthsubstituents. Especially advantageous fat formulations contain, forexample, acetic and butyric acid short chain substituents and a longchain moieties derived from fats having a variety of chain lengths, suchas cottonseed oil. Illustrative formulations are given in the Examples.

Shortening Fats

The low calorie triglycerides of this invention are also especiallyadvantageous in shortening compositions. Preferred shortening fatembodiments contain at least two triglyceride species bearing long,saturated acid residues and propionic acid, butyric acid, mixtures ofacetic and propionic acid, mixtures of acetic acid and butyric acid,mixtures of propionic acid and butyric acid or mixtures of acetic acid,propionic acid, and butyric acid residues. The mixtures can comprisetriglycerides bearing a mixture of short residues or can comprise ablend of triglycerides bearing one species of short residue withtriglycerides bearing another species of short residue.

Typical shortening fat compositions of the invention have the followingsolid fat index:

    ______________________________________                                        Temperatures   Solids (%)                                                     ______________________________________                                        50° F.  at least 25                                                    70° F.  at least 20                                                    80° F.  10 to 50                                                       92° F.  5 to 30                                                        100° F. 0 to 15                                                        ______________________________________                                    

more narrowly the following

    ______________________________________                                        Temperatures   Solids (%)                                                     ______________________________________                                        50° F.  at least 30                                                    70° F.  at least 25                                                    80° F.  15 to 30                                                       92° F.  10 to 20                                                       100° F.  0 to 10                                                       ______________________________________                                    

One embodiment contains R' groups derived from a mixture of acetic andpropionic acid residues. For example, one shortening comprises a mixtureof about 35% diacetyl stearin and about 65% dipropionyl stearin. Anothercomprises a 1:1 mixture of diacetyl stearin and dipropionyl stearin.Another comprises a 1:1 mixture of diacetyl stearin and dibutyrylstearin. Another is prepared by randomly interesterifying, using areactant molar ratio of 1:11:1, triacetin, tripropionin, andhydrogenated canola, hydrogenated soybean oil, or tristearin, and thensteam deodorizing.

Another embodiment contains acetic and butyric R' groups; another,acetic, butyric, and propionic. Yet another contains about 10 to about25 weight percent propionic acid residues. Another has R' groups derivedentirely from propionic acid. Another contains about 10 to about 30weight percent butyric acid residues. Another especially suitable as aspray oil has R' groups derived entirely from butyric acid; one such isprepared by the interesterification of about 12 moles tributyrin and onemole of tristearin or hydrogenated canola.

An advantage of this invention is that the geometry, e.g., height andspread, of finished bakery products containing some preferredembodiments of the shortenings of this invention can be altered byvarying the short chain moieties in the shortening component. Anotheradvantage is that the texture of the finished product can be variedwidely, for example, from a cake-like to a hard snap consistency, bychanging the low calorie shortening component. A further advantage isthat some bakery products containing the shortenings of this inventionretain moisture.

One preferred shortening fat of the invention comprises at least 95%triglycerides bearing one long chain fatty acid residue derived from afat containing at least 90% 18 carbon or higher fatty acid residueshydrogenated to an I.V. value of 3 or less and two short chain residues,each selected from the group consisting of acetic and propionic acidresidues in a molar ratio of 7 to 57, said fat being essentiallytrans-free using A.O.C.S. Method Cd 14-61 and beta crystal free andhaving the following physical properties:

a Mettler Drop point of about 63.7° F. using A.O.C.S. Method Cc 18-80;

a smoke point of about 275° F. using A.O.C.S. Method Cc 9a-48;

a flash point of about 470° F. using A.O.C.S. Method 9a-48;

a fire point of about 495° F. using A.O.C.S. Method 91-48;

a congeal point of about 27.7° C. using A.O.C.S. Method Ca 14-59;

a specific gravity at 60° C. of about 0.9347 using A.O.C.S. Method Cc10b-25;

a peroxide value of about 0.77 meq/kg using A.O.C.S. Method 8-53;

a refractive index at 60° C. of about 1.4398 using A.O.C.S. Method Cc7-25;

a saponification value of about 337 using A.O.C.S. Method 3-25;

an oxidation stability using A.O.C.S. Method Cd 12-57 for at least 290hours;

a free fatty acid value of about 0.45% using A.O.C.S. Method 5a-40;

an S.F.C. of about 68.1% at 50° F., about 43.0% at 70° F., about 5.1% at80° F., about 3.8% at 92° F., and about 4.7% at 100° F. using A.O.C.S.Method Cd 16-81;

a viscosity of about 32.9 cps at 100° F. and about 19.7 cps at 150° F.;

a heat of fusion of about 86.9 mJ/mg;

A Lovibond Color of about 16Red/70Yellow using a 1 inch column followingA.O.C.S. Method Cc 13b-45; and

essentially no crystals exceeding 8 u observed on microscopicexamination under polarized light.

Other Products

The low calorie triglycerides of this invention may advantageously beused in whipped toppings and coffee creamers. Desirable SFI profilevalues for the fat phase of whipped topping mixes are in the followingranges:

    ______________________________________                                        Temperatures   Solids (%)                                                     ______________________________________                                        50° F.  at least 45                                                    70° F.  at least 30                                                    80° F.  15 to 25                                                       92° F.  5 to 20                                                        100° F. 0 to 10                                                        ______________________________________                                    

The triglycerides of this invention are also especially suitable in nutproducts, especially those having at least about 50%, preferably 65% ormore of the nut oil removed and replaced with the low calorie fats.Other exemplary food products which can be improved by the use of thelow calorie triglycerides of this invention are: baked foods, such ascookies, crackers, biscuits, cakes and the like which all contain atleast a flour or starch component in addition to the low calorietriglycerides of this invention; snack products which are fried orcoated with fat or oil and/or also contain at least a flour or starchcomponent in addition to the low calorie triglycerides; emulsionproducts in addition to margarine products such as salad dressing andmayonnaise which all contain emulsions having a fat phase including thelow calorie triglycerides and an aqueous phase; candies and confectionswhich contain a sweetener such as sugar or aspartame in addition to thelow-calorie triglycerides and a flavor such as chocolate; and dairyproduct substitutes which contain a dairy protein such as whey, caseinor caseinate, or the like in addition to the low calorie triglycerides.The margarine products also typically contain a milk component andbutter flavor, while the salad dressings will contain spices and themayonnaise, egg. Among the baked products, cakes and cookies alsocontain sweeteners and the crackers typically contain salt.

EXAMPLES

The following examples are presented to further illustrate and explainthe present invention and should not be taken as limiting in any regard.Unless otherwise indicated, all parts and percentages are by weight, andare based on the weight at the particular stage of the processing beingdescribed. Ratios of short to long (S/L) acid substituents are moleratios.

Nuclear magnetic resonance (NMR) data reported are proton NMR data. NMRS/L ratios are determined as the ratio of intensities of the methyl(--CH₃) resonances for the short and long fatty acid groups,respectively, obtained by dividing the integral areas attributable to Scomponents by the areas attributable to the L, and have experimentalerrors of 5 to 10%. In a typical NMR spectrum at 300 MegaHertz orhigher, the long acid methyl resonance occurs farthest upfield, at ˜0.9ppm, as a triplet. The short acid methyl resonance is structuredependent and occurs at ˜2.00 ppm (acetyl groups), ˜1.15 ppm (propionylgroups) and ˜0.95 ppm (butyryl groups).

Differential scanning calorimetry (DSC) is used to obtain informationabout the melting and crystallization behavior of reduced calorietriglycerides. A liquid sample is cooled from about 20° C. above itsmelting point to about 20° C. below, held at the final temperature, andthen reheated to the initial temperature. Crystallization and meltingthermograms are subjected to several analyses. The melting point(s) aretaken as the peak minima (endothermic transition in the down directionof the chart plotting mW per unit time versus temperature) obtained inthe heating cycle, and the crystallization temperature as the peak onsetin the cooling cycle. Enthalpies of phase transitions are automaticallycalculated in mJoules/mg of sample by choosing the two temperaturepoints of onset of melting and 100% melted. For compound mixturesprepared from natural oils, it is useful to calculate, by integration, asolid fat index in which the percent liquid portion of the sample iscalculated for any temperature. As described hereinafter, this method isemployed where A.O.C.S. Methods Cd 16-81 or Cd 10-57 are not used.

Example 1

Acetyl-distearoyl glyceride (sometimes commonly called acetyldistearin), which comprises a mixture of 1-acetyl-2,3- distearoylglyceride (SLL) and 2-acetyl1,3-distearoyl glyceride (LSL), ##STR13##and which may be used as a component of the fat compositions of thisinvention, is prepared in this example.

One gram of distearin, obtained commercially from Sigma Chemical Co., ischarged to a 100 mL round- bottomed flask equipped with a magnetic stirbar, a reflux condenser, a thermometer, and a heating mantle. To this isadded an excess (15 mL) of acetic anhydride (95%, Aldrich Chemicals),and the mixture is heated to reflux with constant stirring for threehours. After cooling to ambient temperature, the mixture is transferredinto a separatory funnel using 75 mL diethyl ether.

The solution is washed alternatively with 10% sodium bicarbonate andwater until it is neutral to litmus. Finally, the sample is dried at 90°C. for one hour. Analysis of DSC (differential scanning calorimetry)data shows the sample to be 100% solid at 80° F., 98% solid at at 92°F., and 65% solid at 100° F.

Example 2

Other component fats, namely, propionyl-distearoyl glyceride (sometimescommonly called propionyl distearin), a mixture of1-propionyl-2,3-distearoyl glyceride and 2-propionyl-1,3 -distearoylglyceride, which have the following structures, ##STR14## andbutyryl-distearoyl glyceride (sometimes commonly called butyryldistearin), a mixture of 1-butyryl- 2,3-distearoyl glyceride and2-butyryl-1,3-distearoyl glyceride, which have the following structures,##STR15## may be prepared by substituting propionic anhydride andbutyric anhydride, respectively, for acetic anhydride in theesterification of distearin as outlined in Example 1 above.

Example 3

This example illustrates the preparation of another fat,diacetyl-stearoyl glycerol (sometimes commonly called stearoyldiacetin), a mixture of 1,2-diacetyl-3-stearoyl glyceride and1,3-diacetyl-2-stearoyl glyceride, which have the following structures,respectively: ##STR16## One gram of glycerol monostearin, obtainedcommercially from Spectrum Chemicals, is charged to a 100 mLround-bottomed flask equipped with a magnetic stir bar, a refluxcondenser, a thermometer, and a heating mantle. An excess (15 mL) ofacetic anhydride (obtained from Aldrich Chemicals) is added, and themixture heated to reflux for three hours with constant stirring. Aftercooling to ambient temperature, the mixture is transferred to aseparatory funnel using 75 mL diethyl ether.

The solution is washed alternately with 10% sodium bicarbonate and wateruntil it is neutral to litmus and then dried at 90° C. for one hour toafford a mixture of triacylglyceride structures.

Example 4

This example illustrates alternative syntheses of acetyl-distearoylglyceride prepared and illustrated in Example 1 above anddiacetyl-stearoyl glyceride prepared and illustrated in Example 3 above.

To 90 mg (0.14 moles) 1,3-distearin is added 5 mL acetyl chloride, andthe mixture is stirred and heated to 85° C. until all the acetylchloride is reacted. An additional 2 mL acetyl chloride is added and themixture is reheated to yield predominantly 2-acetyl- 1,3-distearoylglyceride.

A mixture of 2.1 g (0.01 mole) stearoyl chloride and 1.4 g (0.01 mole)monoacetin obtained from Kodak is heated to 85° C. for 2 hours. Another4.0 g stearoyl chloride is added and the mixture is reheated to yieldpredominantly 1-acetyl-2,3-distearoyl glyceride.

To 100 mg (0.28 moles) monostearin is added about 5 mL acetyl chloride,and the mixture is stirred and heated to 80° C. in a reaction flask foran hour to yield predominantly 1,2-diacetyl-3-stearoyl glyceride.

Example 5

Other component fats, namely, dipropionyl-stearoyl glyceride, a mixtureof 1,2-dipropionyl-3-stearoyl glyceride and 1,3-dipropionyl-2-stearoylglyceride, which have the following structures, respectively, ##STR17##and dibutyryl-stearoyl glycerol, a mixture of 1,2-dibutyryl-3-stearoylglyceride and 1,3-dibutyryl-2- stearoyl glyceride, which have thefollowing structures ##STR18## may be prepared by substituting propionicanhydride and butyric anhydride, respectively, for acetic anhydride inthe esterification of monostearin as outlined in Example 3 above.

Example 6

In this example, 1,2-dibutyryl-3-stearoyl glyceride (depicted above), atriglyceride component that may be employed in the mixtures of thisinvention, is prepared using an alternate synthetic route employingtributyrin and methyl stearate (Akoh, C. C., and Swanson, B. G., J.Amer. Oil Chem. Soc. 66:1581-1587 (1989)).

A 250-mL, 3-neck flask fitted with a temperature probe, stopper, andvacuum outlet is charged with 52 g (˜0.17 moles) of tributyrin and 52 g(˜0.17 mole) methyl stearate. The mixture is warmed to 48°-50° C. Sodium(2.3 g) is heated in 100 mL xylene to remove sodium oxides and thenadded to the warmed mixture, causing vigorous bubbling. Vacuum isapplied, and the mixture is gradually heated to 110° C. The solutionbecomes yellow, then amber, and, after about 40 minutes, very viscous.Heat is removed, and the reaction mixture is cooled and extracted withhexane (100 mL), ethyl acetate (200 mL), acetic acid (5 mL),hydrochloric acid (10 mL), and (200 mL) water (200 mL). The organiclayer is washed twice with salt water (100 mL), dried over magnesiumsulfate, filtered, and concentrated to obtain a clear, pale yellow oil.The product is purified on a silica gel column eluted with hexane andhexane/ethyl acetate (20:1, v/v).

Example 7

A reduced calorie triglyceride fat mixture of 1-acetyl-2,3-distearoylglyceride, 1,3-diacetyl-2-stearoyl glyceride 2-acetyl-1,3-distearoylglyceride, and 1,2-diacetyl-3-stearoyl glyceride is prepared in thisexample.

One gram of glycerol monostearin and distearin, obtained commerciallyfrom Stephan Chemicals is charged to a 100 mL round-bottomed flaskequipped with a magnetic stir bar, a reflux condenser, a thermometer,and a heating mantle. An excess of acetic anhydride (15 mL, AldrichChemicals) is added, and the mixture heated to reflux with constantstirring for three hours. After cooling to ambient temperature, themixture is transferred to a separatory funnel using 75 mL diethyl ester.

The solution is washed alternately with 10% sodium bicarbonate and wateruntil it is neutral to litmus, and then dried at 90° C. for one hour togive a mixed triacylglyceride composition.

Example 8

Other reduced calorie fat mixtures, such as (i) dipropionyl-stearoylglyceride and propionyl-distearoyl glyceride, a mixture of1,2-dipropionyl-3-stearoyl glyceride, 1,3-dipropionyl-2-stearoylglyceride, 1-propionyl-2,3-distearoyl glyceride, and2-propionyl-1,3-distearoyl glyceride, and (ii) dibutyryl-stearoylglyceride and butyryl-distearoyl glyceride, a mixture of1,2-dibutyryl-3-stearoyl glyceride, 1,3-dibutyryl-2-stearoyl glyceride,1-butyryl-2,3-distearoyl glyceride, and 2-butyryl-1,3-distearoylglyceride, may be prepared by substituting propionic anhydride andbutyric anhydride, respectively, for acetic anhydride in theesterification of monostearin and distearin as outlined in Example 7above.

Example 9

In this example, a triglyceride mixture comprising acetyl-stearoylglycerides of the formulae ##STR19## where the R groups arepredominantly --(CO)(CH₂)₁₆ CH₃ is prepared.

A 3-L, Z-neck reaction flask equipped with a heating mantle, stirrer,thermometer and reflux condenser is charged with 1140 g technical grade(˜40%) monostearin obtained commercially from Stephan, Maywood, N.J.S.F.C. (supercritical fluid chromatography, a quantitative method morecompletely described in Example 21 below) analysis of the startingmaterial reveals 50% monoglyceride, 27% diglyceride and 23%triglyceride. The starting material is melted, 360 g acetic anhydride(˜98% pure, obtained from Aldrich Chemicals) is added, and the mixtureis refluxed under vacuum for 12 hours. During the course of thereaction, 195 g of clear acetic acid is removed.

The golden honey-colored product is purified using a falling-film stillat 180° C., >1 mm Hg to yield a light, soft solid. This is furtherpurified using steam deodorization at 180° C., >1 mm Hg to yield 1113 g(86.3%) bright yellow solid having a capillary melting point of 53° C.NMR analysis shows an S/L ratio of 0.9. S.F.C. analysis (more fullydescribed in Example 21 below) shows 50% of the total composition tocomprise SSL/SLS, 35% LSL/LLS, and 8.4% LLL (with 0.5% monoglyceridesand 5.2% diglycerides).

Example 10

In this example, a propionyl-stearoyl glyceride mixture comprising LSS,SLS, LLS, LSL, and LLL components having the formulae ##STR20## where R'is --(CO)--CH₂ CH₃ and R is --(CO) (CH₂)₁₆ CH₃ is prepared.

A 3-L, 3-neck reaction flask equipped with a heating mantle, stirrer,thermometer and reflux condenser is charged with 1110 g technical grademonostearin obtained commercially from Stephan (which contains mono-,di- and triglycerides as described in Example 9 above). The startingmaterial is melted, 437 g propionic anhydride (˜99% pure, obtained fromAldrich Chemicals) is added, and the mixture is refluxed at 160° C. forabout 15 hours. The mixture is then distilled at 180° C. <100 mm Hg toremove propionic acid.

The product is then purified using a falling-film still at 180° C. anddeodorized at <1 mm Hg, 50 mL H₂ O, 170° C. to yield 1171 g (90.8%) of asoft solid having a capillary melting point of 54° C. NMR analysis showsthe S/L ratio is 0.9. S.F.C. analysis (more fully described in Example21 below) shows the final product contains 55% SSL/SLS, 33% LSL/LLS, and8.2% LLL (with the remainder comprising 0.5% monoglyceride and 3.3%diglyceride).

Example 11

This example describes the preparation of another propionyl-stearoylglyceride mixture like the one described in Example 10 above, exceptthat different proportions of SSL, SLS, LLS, LSL, and LLL components areformed.

A 3-L 3-neck reaction flask equipped with a heating mantle, stirrer,thermometer and reflux condenser is charged with 914 g technical grademonostearin obtained commercially from EM Chemicals (Lot #3006101).S.F.C. analysis of the starting material reveals 54.2% monoglycerides,37.7% diglycerides and 8% triglycerides. The starting material ismelted, 670 g propionic anhydride (˜99% pure, obtained from AldrichChemicals) is added, and the mixture is refluxed at 180° C. for 12hours. The mixture is then distilled at 35 mm Hg to remove propionicacid.

The product is then purified using a falling-film still at 180° C., <1mm Hg and deodorized at 0.5 mm Hg, 45 mL H₂ O, 180° C. to yield 924 g(77%) of a brown soft solid. NMR analysis shows the final product tohave an S/L ratio of 1.2.

Example 12

This example describes an alternate preparation of dipropionyl-stearoylglyceride (depicted in Example 4 above and as SSL and SLS in Examples 10and 11 above).

A 3-L 3-neck reaction flask equipped with a heating mantle, stirrer,thermometer and reflux condenser is charged with 915 g monostearinobtained commercially from Spectrum Chemicals (≧90% pure, Lot #EF027).The starting material is melted, 697 g propionic anhydride (˜99% pure,obtained from Aldrich Chemicals) is added, and the mixture is refluxedfor 18 hours. The mixture is then distilled at <100 mm Hg, 180° C. toremove propionic acid.

The product is purified using a falling film still at 180° C., <1 mm Hg,and deodorized at 0.5 mm Hg, 50 mL H₂ O, 180° C. to yield 1074 g (89.5%)of a clear orange liquid. NMR analysis shows the S/L ratio is 2.1.Analysis of DSC data shows 85% solids at 50° F., 56% solids at 70° F.,8% solids at 80° F., and 0% solids at 92° F.

Example 13

This example describes an alternate preparation of dibutyryl-stearoylglyceride, SLS/SSL triglyceride mixture components depicted in Example 5above.

A distearin starting material is first prepared. A 3-L, 2-neck reactionflask equipped with a heating mantle, thermometer, stirrer, and refluxcondenser is charged with 248 g stearic anhydride (0.45 moles, obtainedfrom Aldrich) and 37 g glycidol (0.5 moles). The mixture is stirred andheated to 95°-100° C. for 3 hours, 3.2 g tetraethylammonium bromide isadded, and the is mixture stirred and heated for another 3 hours at100°-105° C. DL-2-amino-1-propanol (2.4 g) is added and the flask iscooled until i (˜65° C.). The reaction flask is placed in a 60°-65° C.oven, held for 48 hours, and then heated to melt the product fortransfer into a 4-L beaker. The product is crystallized from acetone,washed and dried. A 85% yield of a >93% pure product is obtained.

A 3-L, 3-neck reaction flask equipped with a heating mantle, stirrer,thermometer and reflux condenser is charged with 530 g of the distearinstarting material. This is melted, 144 g butyric anhydride (˜99% pure,obtained from Aldrich Chemicals) is added, and the mixture is refluxedat 180° C. for 8.5 hours. The mixture is distilled at <100 mm Hg, 200°C. to remove butyric acid.

The product is purified using a falling-film still at 180° C., <1 mm Hgand steam deodorized at 0.35 mm Hg, 180° C. to yield 545 g (91%) of alight brown solid having a capillary melting point of 37° to 38° C. NMRanalysis shows the S/L ratio is 0.6.

Example 14

In this example, a butyryl-stearoyl glyceride mixture comprising LSS,SLS, LLS, LSL, and LLL components having the formulae ##STR21## where R'is --(CO)--(CH₂)₂ CH₃ and R is --(CO) (CH₂)₁₆ CH₃ is prepared.

A 3-L, 3-neck reaction flask equipped with a heating mantle, stirrer,thermometer and reflux condenser is charged with 1078 g technical grade(˜40%) monostearin obtained commercially from Stephan (which containsmono-, di- and tristearin as described in Example 9 above). The startingmaterial is melted, 507 g butyric anhydride (˜97% pure, obtained fromAldrich Chemicals) is added, and the mixture is refluxed at 175° C. forabout 15 hours. The mixture is then distilled to remove butyric acid.

The product is then purified using a falling-film still at 120° C., <1mm Hg, and steam deodorized at <1 mm Hg, 50 mL H₂ O, 180° C. to yield1173 g (90.8%) of a soft beige final product having a capillary meltingpoint of 45° C. NMR analysis shows an S/L ratio of 0.9. S.F.C. analysis(more fully described in Example 21 below) shows 56.4% SSL/SLS, 30%LSL/LLS, and 8.7% LLL (with 4.9% diglycerides).

Example 15

This example describes the preparation of another butyryl-stearoylglyceride mixture like the one described in Example 14 above.

A 3-L, 3-neck reaction flask equipped with a heating mantle, stirrer,thermometer and reflux condenser is charged with 864 g technical grademonostearin obtained commercially from EM Chemicals (Lot #3006101,described in Example 11 above). The starting material is melted, 770 gbutyric anhydride (˜99% pure, obtained from Aldrich Chemicals) is added,and the mixture is refluxed at 180° C. for about 12 hours. The mixtureis then distilled to remove butyric acid.

The liquid product is purified using a falling-film still and steamdeodorized at 0.35 mm Hg, 40 mL H₂ O, 180° C. to yield 924 g (77%) of abrown soft solid. NMR analysis shows an S/L ratio of 1.2.

Example 16

This example describes the preparation of another butyryl-stearoylglyceride mixture like the ones described in Examples 13 and 14 above.

A 3-L, 3-neck reaction flask equipped with a heating mantle, stirrer,thermometer and reflux condenser is charged with 864 g monostearinobtained commercially from Spectrum Chemicals (≧90% pure, Lot #EF027).The starting material is melted, 770 g butyric anhydride (˜97% pure,obtained from Aldrich Chemicals) is added, and the mixture is refluxedat 155° C. for about 16 hours. The deep orangered mixture is thendistilled to remove butyric acid.

The milky golden liquid product is purified using a falling-film stilland steam deodorized at <1 mm Hg, 50 mL H₂ O, 180° C. to yield 1041 g(87%) of a yellow golden liquid having a white precipitate. NMR analysisshows an S/L ratio of 2.0. Analysis of DSC data shows 86% solids at 50°F., 13% solids at 70° F., and 0% solids at 80° F.

Example 17

In this example, a blend of predominantly LSL/LLS propionyl-stearoylglyceride and butyryl-stearoyl glyceride (depicted in Examples 10 and 14above) is prepared.

A propionyl-stearoyl glyceride component is prepared by reacting a 1:1molar ratio of distearin with propionic anhydride. A 2-L, 2-neck flaskequipped with a thermometer, reflux condenser, heating mantle andstirrer is charged with 367 g distearin, which is melted prior to adding76 g propionic anhydride. The mixture is refluxed at 125° C. for ˜5hours, left to stand overnight at room temperature, and refluxed withstirring at 80° C. for 6 hours. The mixture is distilled to yield asolid crude product that is dissolved in hexane and washed with wateruntil neutral. Hexane is removed in vacuuo and the off-white productsolid, dried. The yield is 374 g (93%).

A butyryl-stearoyl glyceride component is prepared by reacting distearinwith butyric anhydride (˜99% pure, obtained from Aldrich). A 3-L, 3-neckflask equipped with a thermometer, reflux condenser, heating mantle andstirrer is charged with 720 g distearin, which is half melted prior toadding 204 mL butyric anhydride. The mixture is heated for ˜2 1/2 hoursat 85° C., left to stand without heat for two days, and refluxed at 85°C. for 8 hours. The mixture is distilled twice at 1 mm Hg to yield 743 g(93%) of a hard, light brown solid.

The butyryl-stearoyl glyceride component (650 g) is mixed with thepropionyl-stearoyl glyceride component (350 g) in a 2-L beaker andheated. The blend is steam deodorized at 180° C., 1 mm Hg, 30 mL H₂ O toyield a product having a melting point of 37° to 39° C. and an NMR S/Lratio of 0.6.

Example 18

In this example, another blend of propionyl-stearoyl glyceride andbutyryl-stearoyl glyceride similar to the one prepared in Example 7above, but having a different array of components, is prepared.

A propionyl-stearoyl glyceride component is prepared by reactingdistearin with propionic anhydride. A 3-L, 3-neck flask equipped with astirrer, heating mantle, thermometer, and reflux condenser is chargedwith 500 g of a distearin prepared as set out in Example 13, except thatno 2-amino-propanol and no recrystallization steps are made. NMRanalysis indicates the starting material comprises 90% distearin, 8%tristearain, and 2% monostearin. This is melted prior to adding 111 gpropionic anhydride (Aldrich). The mixture is refluxed 14 hours,distilled, and purified in a falling-film still (<1 mm Hg, 180° C.). Thefinal product, 545 g (95% yield), is a dark brown solid having a meltingpoint of 58° to 60° C.

A butyryl-stearoyl glyceride component is prepared by reacting distearinwith butyric anhydride. A 2-L, 3-neck flask equipped with a stirrer,heating mantle, thermometer, and reflux condenser is charged with 562 gof the distearin employed in the propionyl-stearin synthesis outlinedabove. This is melted prior to adding 150 g butyric anhydride (Aldrich).The mixture is refluxed at reduced pressure 2 hours, distilled, andpurified in a falling-film still (<1 mm Hg, 180° C.). The final product,605 g (96% yield), is a dark brown solid which NMR analysis shows tohave a triglyceride content of 96%.

The propionyl-stearoyl glyceride component (387 g) is melted with thebutyryl-stearoyl glyceride component (721 g) and stirred well. The blendis purified using a steam deodorizer at 0.6 mm Hg, 175° C., 35 mL waterto yield a product comprising 39% propionyl- stearoyl glyceride and 61%butyryl-stearoyl glyceride having an NMR S/L ratio of 0.8.

Example 19

In this example, a blend of predominantly SSL and SLS diacetyl-stearoylglyceride and dipropionyl-stearoyl glyceride components (depicted inExamples 3 and 5 above) is prepared.

An diacetyl-stearoyl glyceride component is prepared by reactingmonostearin with acetic anhydride. A 2-L, 3-neck flask equipped with astirrer, heating mantle, thermometer, and reflux condenser is chargedwith 406 g monostearin obtained from Spectrum Chemicals. This is meltedprior to addition of acetic anhydride (Aldrich), and the mixture isrefluxed at 140° C. for 2 hours, held overnight without heat, andrefluxed for 3 more hours. Acetic acid is distilled off, and the productpurified in a falling film still (1 mm Hg, 180° C.) to yield 438 g (83%)of a golden yellow solid, which NMR show to contain triglycerides only.

A dipropionyl-stearoyl glyceride component is prepared by reactingmonostearin with propionic anhydride. A 3-L, 3-neck flask equipped witha stirrer, heating mantle, thermometer, and reflux condenser is chargedwith 771 g monostearin obtained from Spectrum Chemicals. This is meltedand 552 g propionic anhydride (Aldrich) is added. The mixture isrefluxed 3.5 hours, held overnight without heating, and refluxed 5 morehours. The product is distilled and purified in a falling-film still (<1mm Hg) to yield 935 g (94%) of a clear, golden yellow liquid.

The diacetyl-stearoyl glyceride component (421 g) and thedipropionyl-stearoyl glyceride component (780) are melted together,mixed well, and steam deodorized at 0.6 mm Hg, 168° C., 40 mL H₂ O. Thefinal blend comprises 31% diacetyl- stearin and 69% dipropionyl-stearin,and has an NMR S/L ratio of 1.8.

Example 20

In this example, reduced calorie fat mixtures are prepared byinteresterifying hydrogenated canola (refined, low erucic rapeseed oilcontaining 4% palmitic acid, hydrogenated at 180° C. and 60 lbs hydrogenuntil the Iodine Value (IV) is ≧3) with tributyrin (obtainedcommercially from Eastman Kodak). A Mettler dropping point (M.D.P.) isdetermined for each mixture using a Mettler Thermosystem FP 800following A.O.C.S. Method Cc 18-80 (1989). A solid fat index (S.F.I.) isobtained using A.O.C.S. Method Cd 10-57 (1989). Each mixture issubjected to proton nuclear magnetic resonance (NMR) spectroscopy;integration of the intensities of the various groups gives an estimateof the molar ratio of short (in this case, butyric) to long acids (S/L)present.

One molar equivalent hydrogenated canola (899 g) and 2 to 4.5 molarequivalents tributyrin are interesterified in the presence of 0.2 to0.3% sodium methoxide by heating to ˜110° C. with agitation under avacuum for about half an hour until color develops. (The M.D.P. may bechecked at this time, and the reaction continued if the M.D.P. has notdropped sufficiently.) Phosphoric acid (˜0.2 to ˜0.5%, at least twicethe amount of sodium methoxide) is added to stop each reaction andneutralize the mixture, followed by the addition of 0.5% activatedbleaching clay (Tonsil Optimum FF), 0.5% diatomaceous earth, and 1000ppm citric acid (dissolved in water) to decolorize and remove soaps. Thetreatment is continued for 1/2 to 1 hour at 110° C. The products arecooled to 80° C., filtered, bleached, and steam deodorized at 210° C.for 2 to 3 hours.

Using this procedure, a 1:25 molar reactant ratio of hydrogenated canolato tributyrin yields a liquid product having a M.D.P. of 18.6° C. and anNMR S/L of 2.0. Conversely, a 1:0.5 molar ratio yields a waxy producthaving a M.D.P. of 63.0° C. and an NMR S/L of 0.5; similarly, a 1:1molar ratio of hydrogenated canola to tributyrin yields a product havinga M.D.P. of 57.9° C. and an NMR S/L of 0.8. Using intermediate reactantratios, the following triglyceride mixtures are obtained:

    ______________________________________                                        Hydrogenated Canola:Tributyrin Reactant Molar Ratio                                  1:2   1:2.5  1:3     1:3.5                                                                              1:4   1:4.5                                                                              1:12                              ______________________________________                                        M.D.P., °C.                                                                     35.1    31.8   30.4  28.7 27.5  26.6 22.1                            S.F.I.                                                                        50° F.                                                                          68.8    69.5   66.8  63.6 63.8  63.4 54.3                            70° F.                                                                          52.3    53.6   39.6  33.1 29.8  24.7 3.8                             80° F.                                                                          24.0    23.7   8.8   4.7  3.9   2.1  0.0                             92° F.                                                                          10.0    9.2    4.3   3.2  2.3   1.6  0.0                             100° F.                                                                         9.2     8.8    4.0   2.6  0.0   0.0                                  NMR S/L  1.2     1.2    1.3   1.4  1.5   1.4  1.8                             ______________________________________                                    

Example 21

This example illustrates a method of analyzing hydrogenatedcanola/tributyrin triglyceride mixtures prepared in Example 20 usingsupercritical fluid chromatography (S.F.C.) to separate and quantify themixture components.

After filtering through a 0.45 micron filter, 0.1 ul of a 30 to 50 mg/mlsample is injected onto a 1×100 mm Deltabond Cyano™ column from KeystoneScientific in a Suprex Model 200A S.F.C. having an S.F.C.- grade carbondioxide mobile phase and an oven temperature of 125° C. A linearpressure gradient of 100 to 300 atmospheres is applied over a course of20 minutes (i.e., 10 atm/min), followed by a hold at 300 atmospheres for10 minutes. A flame ionization detector at 400° C. detects emergingmixture components run against an internal standard of methyltetradecanoate (10 to 12 mg/mL) in methylene chloride. Externalstandards of mono, di, and tristearin (˜10 mg/mL each) are run underidentical conditions. Using these peak areas, the peak areas. of thesample are normalized, added together, and divided by the total toobtain the following percentages of LSS & SLS, LLS & LSL, and LLL in themixtures:

    ______________________________________                                        Hydrogenated Canola:Tributyrin Reactant Molar Ratio                                  1:0.5                                                                              1:1    1:2    1:2.5                                                                              1:3  1:3.5                                                                              1:4  1:4.5                           ______________________________________                                        % LSS/SLS                                                                              17.0   39.2   57.2 67.2 69.4 73.2 78.1 80.2                          % LLS/LSL                                                                              38.5   43.8   34.7 28.8 27.1 24.0 20.5 18.4                          % LLL    44.5   17.1   8.1  4.0  3.4  2.7  1.4  1.4                           ______________________________________                                    

The mixtures prepared in Example 20 thus include, after purification,compounds of the formula ##STR22## where R' is --(CO)--(CH₂)₂ CH₃ and Ris derived from hydrogenated canola oil

Example 22

In this example, reduced calorie fat mixtures are prepared byinteresterifying one mole hydrogenated canola (obtained as described inExample 20) with 2.5, 3.5, or 12 moles tripropionin (obtainedcommercially from Pfaltz & Bauer).

Using the preparative and analytical procedures outlined in Example 20,the following M.D.P., S.F.I., and NMR S/L data on the products areobtained:

    ______________________________________                                        Hydrogenated Canola:Tripropionin Reactant Molar Ratio                                   1:2.5      1:3.5  1:12                                              ______________________________________                                        M.D.P., °C.                                                                        34.4         33.5   27.2                                          S.F.I.                                                                        50° F.                                                                             70.6         61.7   54.9                                          70° F.                                                                             66.1         56.5   32.2                                          80° F.                                                                             51.2         35.5   0.8                                           92° F.                                                                             7.3          0.0    0.0                                           100° F.                                                                            4.3          0.0    0.0                                           NMR S/L     1.2          1.4    2.2                                           ______________________________________                                    

Example 23

Reduced calorie fat mixtures are prepared as described in Example 22,except that the interesterification mixture contains hydrogenated canola(obtained as described in Example 20) with both tripropionin (1.25,1.75, and 6 moles to 1 mole hydrogenated canola) and tributyrin (in thesame proportions).

Using the preparative and analytical procedures outlined in Example 22,the following M.D.P., S.F.I., and NMR S/L data on the products areobtained:

    ______________________________________                                        Hydrogenated Canola:Tributyrin:Tripropionin                                   Reactant Molar Ratio                                                                   1:1.25:1.25                                                                              1:1.75:1.75                                                                             1:6:6                                           ______________________________________                                        M.D.P., °C.                                                                       32.5         30.0      24.4                                        S.F.I.                                                                        50° F.                                                                            67.7         65.0      51.7                                        70° F.                                                                            54.0         44.6      13.8                                        80° F.                                                                            28.1         16.6      0.0                                         92° F.                                                                            4.7          1.4       0.0                                         100° F.                                                                           4.4          2.3       0.0                                         NMR S/L    1.3          1.5       2.1                                         ______________________________________                                    

Example 24

Reduced calorie fat mixtures are prepared as described in Examples 20and 23, except that the interesterification mixture containshydrogenated canola with both tripropionin (1.25 moles, 2.25 moles and 6moles per mole hydrogenated canola) and triacetin (in the sameproportions), the reaction temperature is 120° to 125° C., and 0.5%sodium methoxide is employed.

Using the preparative and analytical procedures outlined in Example 22,the following M.D.P. and S.F.I. data on the products are obtained:

    ______________________________________                                        Hydrogenated Canola:Tripropionin:Triacetin                                    Reactant Molar Ratio                                                                   1:1.25:1.25                                                                              1:2.25:2.25                                                                             1:6:6                                           ______________________________________                                        M.D.P., °C.                                                                       36.8         33.8      31.4                                        S.F.I.                                                                        50° F.                                                                            71.4         69.8      54.8                                        70° F.                                                                            69.8         56.0      34.2                                        80° F.                                                                            64.3         1.5       0.0                                         92° F.                                                                            23.0         0.0       0.0                                         100° F.                                                                           0.2          0.0       0.0                                         NMR S/L    1.3          1.6       2.1                                         ______________________________________                                    

Example 25

Reduced calorie fat mixtures are prepared as described in Examples 20and 23, except that the interesterification mixture containshydrogenated canola (denoted below as "H-Canola") with triacetin,tripropionin, and tributyrin (in proportions set out below).

Using the preparative and analytical procedures outlined in Example 22,the following M.D.P. and S.F.I. data on the products are obtained:

    ______________________________________                                        H-Canola:Triacetin:Tripropionin:Tryibutyrin                                   Molar Reactant Ratio                                                                   1:0.5:1.0:1.0                                                                           1:0.7:1.4:1.4                                                                           1:2.4:4.8:4.8                                    ______________________________________                                        M.D.P., °C.                                                                       35.0        31.3      26.8                                         S.F.I.                                                                        50° F.                                                                            68.6        67.8      63.3                                         70° F.                                                                            63.2        56.5      36.1                                         80° F.                                                                            42.5        29.6      1.0                                          92° F.                                                                            4.6         0.0       0.0                                          100° F.                                                                           4.6         0.0       0.0                                          NMR S/L    1.4         1.6       2.1                                          ______________________________________                                    

Example 26

This example illustrates how the triglyceride mixtures of this inventionare screened for caloric availability by a carefully controlled in vivoanimal feeding study.

An experimental relationship between oil calories ingested and animalbody weight gain is established by monitoring the body weight gainassociated with consumption of a nutritionally balanced diet containingvarying concentrations of a reference substance such as corn oil whichhas a known caloric availability. Correlations between total caloriesingested and body weight gain are excellent (r=0.99).

Caloric availability of an unknown substance is evaluated bysubstituting a specific weight of the unknown substance for thereference substance and observing the body weight gain. The gain in bodyweight is equated to a total number of calories using the correlationpreviously established for the reference data. The estimated number ofcalories ingested are divided by the weight of unknown substance to givethe apparent calories metabolized per gram for the unknown substance.

The test animals are weanling male Sprague-Dawley rats, weighingapproximately 50 to 60 g prior to acclimation. After acclimation for 3to 10 days, the test duration is 14 days. The dietary requirements areestablished by observing the actual feed consumption of animals providedwith unlimited feed. All diets are prepared to contain 50% of theestablished dietary requirements plus any supplements of reference orunknown substances. In all tests so designed the test animals aremaintained in very good health.

The animals are housed singly in suspended wire mesh cages which conformto the size recommendatins in the Guide for the Care and Use ofLaboratory Animals, Department of Health, Education and Welfare,National Institute of Health Bulletin No. 78.23. Litter paper is changedat least three times a week. The animal room is temperature controlled,with a 12-hour light/dark cycle, and kept clean and vermin free. Wateris provided ad-libitum.

There are ten animals per group. The test feeds are NIH 07 Open FormulaRodent Chow diets manufactured by Zeigler Bros., obtained as pellets ormeal. Fortified diets employ 0.2% AIN-76A vitamin pre-mix obtained fromTeklad. Weight gains are measured at days 0, 3, 7, 10, and 14 .

The test groups are as follows:

    ______________________________________                                        Group Test Diet         Feeding Regimen                                       ______________________________________                                        1     NIH-07            Ad-libitum                                            2     NIH-07            Pair Fed 50% of Gp. 1                                 3     As Gp. 2 + 7% corn oil                                                                          Pair Fed 50% of Gp. 1                                 4     As Gp. 2 + 14% corn oil                                                                         Pair Fed 50% of Gp. 1                                 5     As Gp. 2 + 21% corn oil                                                                         Pair Fed 50% of Gp. 1                                 ______________________________________                                    

Rats were fed a diet of 21% triglyceride test substances prepared asdescribed in the above Examples as test compounds under the foregoingprocedure, and their weight gains were determined. Based upon the baseline corn oil control data, and the data from the test substances, thefollowing caloric availability data (expressed as kcal/gram) weredetermined:

    ______________________________________                                        Low Calorie Triglycerides    kcal/g                                           ______________________________________                                        Example 9 Acetyl-stearoyl Glycerides (S/L = 0.9)                                                           3.9                                              Example 10 Propionyl-stearoyl Glycerides (S/L = 0.9)                                                       3.9                                              Example 11 Propionyl-stearoyl Glycerides (S/L = 1.3)                                                       4.4                                              Example 12 Propionyl-stearoyl Glycerides (S/L = 11.0)                                                      4.1                                              Example 14 Butyryl-stearoyl Glycerides (S/L = 0.9)                                                         4.0                                              Example 15 Butyryl-stearoyl Glycerides (S/L = 1.1)                                                         4.4                                              Example 16 Butyryl-stearoyl Glycerides (S/L = 1.9)                                                         4.2                                              Example 17 Butyryl/propionyl-stearoyl Glycerides                                                           3.1                                              Example 18 Butyryl/propionyl-stearoyl Glycerides                                                           1.7                                              Example 19 Acetyl/propionyl-stearoyl Glycerides                                                            4.8                                              Example 20 1:1 Hydrogenated Canola/Tributyrin                                                              3.6                                              Example 20 1:2 Hydrogenated Canola/Tributyrin                                                              3.9                                              Example 20 1:2.5 Hydrogenated Canola/Tributyrin                                                            3.9                                              Example 20 1:3 Hydrogenated Canola/Tributyrin                                                              3.8                                              Example 20 1:3.5 Hydrogenated Canola/Tributyrin                                                            3.8                                              ______________________________________                                    

Example 27

This example describes feeding studies using the method described inExample 26 above, except that rats were fed a diet of 21%, 15%, 10% and5% triglyceride test substance. The test substance is a triglyceridemixture obtained by the interesterification of hydrogenated canola andtributyrin in a 1:2.5 molar ratio as described in Example 20.

Caloric availability is estimated by comparing weight gain of rapidlygrowing male rats fed corn oil compared to weight gain of rats fed thetest oil.

To conduct the experiment, a group of 10 rats are fed NIH-07 openformula died ad libitum. This group is started on the diet one day aheadof all the others. Each day the feed consumption for the ad libitumgroup is determined.

All experimental groups receive 50% of the NIH-07 diet consumed on theprevious day. The standard curve for growth is developed bysupplementing the NIH-07 diets with various levels of corn oil (0, 5,10, 15 and 21%). The mean body weight gain for each corn oilsupplemented sample is regressed against the calories from corn oil(feed consumption * % corn oil * 9) for 0, 5, 10, and 15% corn oil toestablish the equation of the standard curve. The 21% corn oil weightgain is dropped from the standard curve calculation because the responseis not linear at that level (the animals being saturated with amount offat in the diet). The weight gain for rats consuming test oil arecompared to the standard curve, and calories are calculated using theformula: ##EQU1## The following caloric availability are obtained:

    ______________________________________                                        Dietary Level   kcal/g                                                        ______________________________________                                         5%             4.6.sup.a                                                     10%             6.0.sup.b                                                     15%             5.8.sup.a                                                     21%             4.6%.sup.c                                                    ______________________________________                                         .sup.a Average of results obtained from two feeding studies.                  .sup.b Average of results obtained from six feeding studies. Rats fed the     same diet having a calcium supplement exhibited a calculated caloric          availability of 5.0 kcal/gram (an average of three feeding studies).          .sup.c Average of results obtained from four feeding studies.            

Example 28

In this example, reduced calorie fat mixtures are prepared using theprotocol described in Example 20 by interesterifying hydrogenated canolaand tributyrin. With a 1:12 molar reactant ratio of hydrogenated canolato tributyrin, a product with an M.D.P. of 22.5° C. and an NMR S/L ratioof 1.8 was obtained; the S.F.I. is 50.7% at 50° F., 3.9% at 70° F., and0% at 80%. Increasing the proportion of tributyrin to 1:25 yielded aproduct with an M.D.P. of 18.6° C. and an NMR S/L ratio of 2.0; theS.F.I. is 1.7% at 50° F., 2.6% at 70° F., and 0% at 80° F.

Example 29

In this example, reduced calorie fat mixtures are prepared using theprotocol described in Example 20 by interesterifying one mole fullyhydrogenated high erucic rapeseed oil (obtained from CSP) with 2.5, 4.0,or 12 moles tripropionin (obtained commercially from Pfaltz & Bauer).

Using the preparative and analytical procedures outlined in Example 20,the following M.D.P., S.F.I., and NMR S/L data on the products areobtained:

    ______________________________________                                        Hydrogenated Rapeseed:Tripropionin Reactant Molar Ratio                                 1:2.5      1:4    1:12                                              ______________________________________                                        M.D.P., °C.                                                                        44.6         42.5   39.2                                          S.F.I.                                                                        50° F.                                                                             79.3         76.7   68.7                                          70° F.                                                                             74.9         72.0   61.8                                          80° F.                                                                             73.6         68.9   52.8                                          92° F.                                                                             60.4         48.7   24.9                                          100° F.                                                                            38.7         25.0   3.5                                           NMR S/L     1.2          1.5    1.9                                           ______________________________________                                    

Example 30

In this example, reduced calorie fat mixtures are prepared using theprotocol described in Example 20 by interesterifying one mole fullyhydrogenated menhaden fish oil (obtained from Zapata Hayne) with 2.5,4.0, or 12 moles tripropionin (obtained commercially from Pfaltz &Bauer).

Using the preparative and analytical procedures outlined in Example 20,the following M.D.P., S.F.I., and NMR S/L data on the products areobtained:

    ______________________________________                                        Hydrogenated Fish Oil:Tripropionin Reactant Molar Ratio                                 1:2.5      1:4    1:12                                              ______________________________________                                        M.D.P., °C.                                                                        32.7         31.3   25.9                                          S.F.I.                                                                        50° F.                                                                             60.5         55.7   40.6                                          70° F.                                                                             41.8         32.4   13.3                                          80° F.                                                                             22.2         12.3   0.2                                           92° F.                                                                             3.0          0.0    0.0                                           100° F.                                                                            0.3          0.0    0.0                                           NMR S/L     1.1          1.4    2.0                                           ______________________________________                                    

Example 31

Using the procedure outlined in Example 20, tributyrin isinteresterified with safflower oil obtained from Welch, Holme, andClark. A liquid oil (having no solids at 50° F. to 100° F.) is obtainedwith oil to tributyrin reactant molar ratios of 1:2.5, 1:4, and 1:12.

Example 32

Using the procedure outlined in Example 20, tripropionin isinteresterified with safflower oil. A liquid oil (having no solids at50° to 100° F.) is obtained with oil to tributyrin reactant molar ratiosof 1:2.5, 1:4, and 1:12.

Example 33

In this example, reduced calorie fat mixtures are prepared using theprotocol described in Example 20 by interesterifying hydrogenated canolaoil with tripropionin and safflower oil.

With a safflower:hydrogenated canola:tripropionin reactant molar ratioof 0.66:0.33:12, and oil with no solids at 50° to 100° F. is obtained.Using the preparative and analytical procedures outlined in Example 20,the following S.F.I. data on products prepared using other ratios areobtained:

    ______________________________________                                        Safflower:Hydrogenated Canola:Tripropionin                                    Reactant Molar Ratio                                                          S.F.I.   0.33:0.66:2.5                                                                              0.33:0.66:12                                                                            0.66:0.33:2.5                                 ______________________________________                                        50° F.                                                                          24.1         16.0      1.5                                           70° F.                                                                          4.7          0.2       0                                             80° F.                                                                          1.2          0                                                       92° F.                                                                          0.6                                                                  100° F.                                                                         0                                                                    ______________________________________                                    

Example 34

Using the feeding study protocol set out in Example 26, rats were fed adiet of 21% triglyceride test substances prepared as described in theprevious Examples as test compounds. As used herein, hydrogenated canolais abbreviated "H-Canola." Based upon the base line corn oil controldata, and the data from the test substances, the following caloricavailability data (expressed as kcal/gram) were calculated as describedin Example 27:

    ______________________________________                                        Low Calorie Triglycerides   kcal/g                                            ______________________________________                                        Ex. 22 Hydrogenated Canola/Tripropionin (S/L = 1.2)                                                       4.7                                               Ex. 22 Hydrogenated Canola/Tripropionin (S/L = 1.3)                                                       4.3                                               Ex. 22 Hydrogenated Canola/Tripropionin (S/L = 2.2)                                                       4.7                                               Ex. 23 H-Canola/Tripropionin/Tributyrin (S/L = 1.3)                                                       4.8                                               Ex. 23 H-Canola/Tripropionin/Tributyrin (S/L = 1.5)                                                       4.8                                               Ex. 23 H-Canola/Tripropionin/Tributyrin (S/L = 2.1)                                                       5.6                                               Ex. 24 H-Canola/Triacetin/Tripropionin (S/L = 1.3)                                                        5.0                                               Ex. 24 H-Canola/Triacetin/Tripropionin (S/L = 1.6)                                                        5.0                                               Ex. 24 H-Canola/Triacetin/Tripropionin (S/L = 2.1)                                                        5.4                                               Ex. 25 S/L 1.4                                                                H-Canola/Triacetin/Tripropionin/Tributyrin                                                                5.2                                               Ex. 25 S/L 1.6                                                                H-Canola/Triacetin/Tripropionin/Tributyrin                                                                5.3                                               Ex. 25 S/L 2.1                                                                H-Canola/Triacetin/Tripropionin/Tributyrin                                                                5.7                                               Ex. 28 1:12 Hydrogenated Canola/Tributyrin                                                                5.2                                               (S/L = 1.8)                                                                   Ex. 28 1:25 Hydrogenated Canola/Tributyrin                                                                6.2                                               (S/L = 2.0)                                                                   Ex. 31 Safflower/Tributyrin (S/L = 0.9)                                                                   6.7                                               Ex. 31 Safflower/Tributyrin (S/L = 1.1)                                                                   6.6                                               Ex. 31 Safflower/Tributyrin (S/L = 1.5)                                                                   6.7                                               Ex. 32 Safflower/Tripropionin (S/L = 1.2)                                                                 6.9                                               Ex. 32 Safflower/Tripropionin (S/L = 1.3)                                                                 6.5                                               Ex. 32 Safflower/Tripropionin (S/L = 2.0)                                                                 6.0                                               ______________________________________                                    

Example 35

Using the feeding study protocol set out in Example 26, rats were fed adiet of 10% triglyceride test substances prepared as described in theabove Examples as test compounds. As used herein, hydrogenated canola isabbreviated "H-Canola" and hydrogenated high erucic rapeseed isabbreviated "H-Rapeseed." Based upon the base line corn oil controldata, and the data from the test substances, the following caloricavailability data (expressed as kcal/gram) were calculated as describedin Example 27:

    ______________________________________                                        Low Calorie Triglycerides    kcal/g                                           ______________________________________                                        Example 20 1:2.5 H-Canola/Tributyrin and Triacetin                                                         3.3                                              Example 20 1:2.5 H-Canola/Tributyrin and Triacetin                                                         3.9                                              Example 29 H-Rapeseed/Tripropionin (S/L 1.2)                                                               3.8                                              Example 29 H-Rapeseed/Tripropionin (S/L 1.5)                                                               4.1                                              Example 29 H-Rapeseed/Tripropionin (S/L 1.9)                                                               5.7                                              Example 30 Hydrogenated Fish Oil/Tripropionin                                                              7.0                                              (S/L 1.2)                                                                     Example 30 Hydrogenated Fish Oil/Tripropionin                                                              7.4                                              (S/L 1.4)                                                                     Example 30 Hydrogenated Fish Oil/Tripropionin                                                              6.6                                              (S/L 2.0)                                                                     Example 33 H-Canola/Safflower/Tripropionin (S/L 1.2)                                                       6.8                                              Example 33 H-Canola/Safflower/Tripropionin (S/L 1.5)                                                       6.3                                              Example 33 H-Canola/Safflower/Tripropionin (S/L 1.9)                                                       7.0                                              Example 33 H-Canola/Safflower/Tripropionin (S/L 11.0)                                                      7.3                                              ______________________________________                                    

Example 36

Reduced calorie fat mixtures are prepared as described in Example 24,except that the interesterification mixture contains differentproportions of hydrogenated canola (abbreviated "H-Canola"),tripropionin and triacetin. Using the preparative and analyticalprocedures outlined in Example 22, the following M.D.P. and S.F.I. dataon the products are obtained:

    ______________________________________                                        H-Canola:Tripropionin:Triacetin                                               Reactant Molar Ratio                                                                         1:1:11                                                                              1:11:1                                                   ______________________________________                                        M.D.P., °C.                                                                             35.0    17.6                                                 S.F.I.                                                                        50° F.    64.4    55.0                                                 70° F.    62.4    32.3                                                 80° F.    58.7    7.4                                                  92° F.    28.5    0.0                                                  100° F.   0.4     0.0                                                  NMR S/L          1.8     1.8                                                  ______________________________________                                    

Example 37

This example details the physical and chemical characterization ofseveral reduced calorie triglyceride mixtures of this invention. MixtureA is prepared by the interesterification of 2.5 moles tributyrin with 1mole hydrogenated canola as outlined in Example 20. The M.D.P.determined using A.O.C.S. Method Cc 18-80 is 30.9° C. and the S.F.I.obtained using A.O.C.S. Method Cd 10-57 shows 64.8% solids at 50° F.,38.7% at 70° F., 11.4% at 80° F., 4.9% at 92° F., and 5.2% at 100° F.Mixture B is prepared by the interesterification of 11 moles oftriacetin and 1 mole tripropionin with 1 mole of hydrogenated canola,and mixture C is prepared by the interesterification of 1 mole oftriacetin and 11 moles of tripropionin with 1 mole of hydrogenatedcanola as described in Example 36.

Viscosity is determined using a Haake viscometer, Rotovisco visco™ modelRV12, with a M-500 measuring head consisting of a sensor system cup anda bell shaped rotor that are manually attached to a temperature vessel,then connected to a circulator and a temperature controlled waterbath.The method measures simple shear at two temperatures in the annular gapbetween two concentric cylinders. Continuous measurements of torque atzero up to 100 rpm are recorded on a chart from which viscosity of theliquid fat is calculated.

In the practice of viscosity determinations, the sample is melted (ifnot already liquid) and stirred thoroughly; the temperature duringmelting does not exceed the melting point of the sample by more than 10°C. For each temperature, the measured value (S) from the chart is readat the point that intercepts the curve at 50 rpm and the viscositycalculated using the following equation: ##EQU2## where G is a constantinstrument factor dependent on the torque of the measuring drive unitand the geometry of the sensor system (329 with the 4.0 Sensor System NVand the equipment described herein);

S is the measured value in scale units (from the chart); and

n is the test speed in rpm at the measured value.

Fatty acids are determined using proton NMR as described heretofore,with results denoted in Table I following using the abbreviation "but."for butyric acid, "ac." for acetic acid, "pro." for propionic acid, and"st." for stearic acid. Short/long chain ratios are also determinedusing proton NMR, and the heats of fusion are determined using DSC asdescribed heretofore. The other measurements follow A.O.C.S. methods aslisted; Lovibond Color is assayed using a 1 inch column.

Using these analytical techniques the following data are obtained:

                                      TABLE I                                     __________________________________________________________________________               Reduced Calorie Triglyceride Mixture                               Properties Method  A     B     C                                              __________________________________________________________________________    Fatty acids              51% ac.                                                                             7% ac.                                         (mole %)   Proton  54% but.                                                                            13% pro.                                                                            57% pro.                                                  NMR     46% st.                                                                             36% st.                                                                             36% st.                                        Short/Long Proton  1.2   1.8   1.8                                            Chain Ratio                                                                              NMR                                                                Mettler    AOCS Method                                                                           87.6° F.                                                                     95.0° F.                                                                     63.7° F.                                Drop Point Cc 18-80                                                           Smoke Point                                                                              AOCS Method                                                                           310° F.                                                                      260° F.                                                                      275° F.                                            Cc 9a-48                                                           Flash Point                                                                              AOCS Method                                                                           480° F.                                                                      470° F.                                                                      470° F.                                            Cc 9a-48                                                           Fire Point AOCS Method                                                                           510° F.                                                                      495° F.                                                                      495° F.                                            Cc 9a-48                                                           Peroxide Value                                                                           AOCS Method                                                                           0.20  0.45  0.77                                                      Cd 8-53 meq/kg                                                                              meq/kg                                                                              meq/kg                                         Free Fatty Acids                                                                         AOCS Method                                                                           0.23% 0.78% 0.45%                                                     Ca 5a-40                                                           Congeal Point                                                                            AOCS Method                                                                   Cc 14-59                                                                              30.6° C.                                                                     33.8° C.                                                                     27.7° C.                                Sp. Gravity @ 60° C.                                                              AOCS Method                                                                           0.9097                                                                              0.9337                                                                              0.9347                                                    Cc 10-23                                                           Refract index                                                                            AOCS Method                                                                           1.4396                                                                              1.4385                                                                              1.4398                                         @ 60° C.                                                                          Cc 7-25                                                            Saponification                                                                           AOCS Method                                                                           287   347   337                                            Value      Cd 3-25                                                            AOM Oxidative                                                                            AOCS Method                                                                           295.sup.+  hrs                                                                      290.sup.+ hrs                                                                       290.sup.+  hrs                                 Stability  Cd 12-57                                                           Solid Fat  AOCS Method                                                                           78.2% 82.1% 68.1%                                          Content @ 50° F.                                                                  Cd 16-81                                                           Solid Fat  AOCS Method                                                                           49.3% 78.4% 43.0%                                          Content @ 70° F.                                                                  Cd 16-81                                                           Solid Fat  AOCS Method                                                                           11.8% 71.7% 5.1%                                           Content @ 80° F.                                                                  Cd 16-81                                                           Solid Fat  AOCS Method                                                                           7.3%  29.9% 3.8%                                           Content @ 92° F.                                                                  Cd 16-81                                                           Solid Fat  AOCS Method                                                                           7.8%  4.9%  4.7%                                           Content @ 100° F.                                                                 Cd 16-81                                                           Viscosity @ 100° F.                                                               Haake   32.9 cps                                                                            35.1 cps                                                                            32.9 cps                                                  Viscometer                                                         Viscosity @ 150° F.                                                               Haake   26.3 cps                                                                            19.7 cps                                                                            19.7 cps                                                  Viscometer                                                         Lovibond Color                                                                           AOCS Method                                                                           8 Red/                                                                              20 Red/                                                                             16 Red/                                                   Cc 13b-45                                                                             79 Yellow                                                                           77 Yellow                                                                           70 Yellow                                      Heat of Fusion                                                                           DSC     121.6 99.4  86.9                                                              mJ/mg mJ/mg mJ/mg                                          __________________________________________________________________________

Example 38

This example compares the melting point behavior of monostearinderivatives as a function of chain length. Each derivative bears onestearic acid residue per molecule and two identical short or mediumchain substituents.

Diacetyl monostearin is prepared by melting 968.22 g (2.7 moles)1-glycerol-rac-monostearin obtained from Spectrum Chemicals (Lot #FC026)in a reaction flask equipped with a magnetic stirrer, heating mantle,thermometer, and reflux condenser prior to adding 578.85 g (5.67 moles)acetic anhydride (Aldrich Chemicals). The reaction flask is heated to140° C. for 5 hours at atmospheric pressure, and the acetic acid sideproduct is removed by vacuum distillation at 90 mm Hg, 95° C. The yieldof distillate is quantitative. The dark brown waxy product isdecolorized with activated charcoal and heptane for 10 hours; thecarbon, removed with hot vacuum filtration; and heptane, removed byvacuum, yielding a golden yellow waxy product which is passed through afalling film still equipped with mesitylene as the boiling solvent (168°C., <1 mm Hg) and deodorized. The yield is 2.52 moles (92.9%) of agolden yellow wax having a capillary melting point of 35°-36° C. and aDSC melting point of 35. NMR in CDCl₃ (chemical shifts in ppm): 5.25 (m,1 H), 4.3 (dd, 2 H), 4.15 (dd, 2 H), 2.3 (m, 2 H), 2.1 (m, 6 H), 1.6 (m,2 H), 1.3 (m, 28 H), 0.9 (t, 3H).

Dipropionyl monostearin is prepared by melting 771 g (2.15 moles)1-glycerol-rac-monostearin obtained from Spectrum Chemicals (Lot #FC026)in a 2-L reaction flask equipped with a magnetic stirrer, heatingmantle, thermometer, and reflux condenser prior to adding 552 g (4.24moles) propionic anhydride (Aldrich Chemicals). The reaction flask isheated to 167° C. for 8 hours at atmospheric pressure, and the sideproduct removed by vacuum distillation at 65 mm Hg, 85° C. The goldenyellow solf solid product is passed through a falling film stillequipped with mesitylene as a boiling solvent (168° C., <1 mm Hg) anddeodorized to afford 935.5 g (1.98 moles, 94%) of a golden yellow softsolid having a DSC melting point of 24° C. SFC analysis: 96.5% SPP/PSP,3.3% SPS/SSP, 0.2% SSS, <<1% unreacted material. NMR in CDCl₃ (chemicalshifts in ppm): 5.25 (m, 1 H), 4.3 (dd, 2 H), 4.15 (dd, 2 H), 2.35 (m, 6H), 1.6 (m, 2 H), 1.25 (m, 28 H), 1.1 (m, 6 H), 0.9 (t, 3 H).

Dibutyryl monostearin is prepared by melting 864.2 g (2.47 moles)1-glycerol-rac-monostearin obtained from Spectrum Chemicals (Lot #FC026)in a 2-L reaction flask equipped with a magnetic stirrer, heatingmantle, thermometer, and reflux condenser prior to adding 770.4 g (4.87moles) butyric anhydride (Aldrich Chemicals). The reaction flask isheated to 180° C. for 16 hours at atmospheric pressure, and the butyricacid side product is removed by vacuum distillation at 100 mm Hg, 105°C. The yield of distillate is quantitative. The milky golden liquidproduct is passed through a falling film still equipped with mesitylneas the boiling solvent (168° C., <1 mm Hg) and steam deodorized at 210°C., <1 mm Hg. The yield is 2.08 moles (86.8%) of a golden yellow verysoft solid having a DSC melting point of 21° C. SFC analysis: 94.2%SBB/BSB, 5.3% SBB/BSB, 4% 1-monostearin. NMR in CDCl₃ (chemical shiftsin ppm) indicates 95% product: 5.25 (m, H) , 4.3 (dd, 2 H), 4.15 (dd, 2H), 2.35 (m, 6 H), 1.6 (m, 6 H), 1.25 (m, 28 H), 1.1 (m, 6 H), 0.9 (t, 3H).

Dihexanyl monostearin is prepared by melting 775.5 g (4.32 moles)1-glycerol-rac-monostearin obtained from Spectrum Chemicals (Lot #FC026)in a 2-L reaction flask equipped with a magnetic stirrer, boiling chips,heating mantle, thermometer, and reflux condenser prior to adding 775.5g (2.16 moles) hexanoic anhydride (Aldrich Chemicals). The reactionflask is heated to 250° C. for 8 hours at atmospheric pressure, and thehexanoic acid side product is removed by vacuum distillation at >1 manHg, 70° C. The yield of distillate is quantitative. The product ispassed through a falling film still equipped with mesitylne as theboiling solvent (168° C., <1 mm Hg) and steam deodorized at 210° C., <1mm Hg. The yield is 2.12 moles (97.9%) of a golden yellow very softsolid having a DSC melting point of 13° C. NMR in CDCl₃ (chemical shiftsin ppm) indicates 99% product: 5.25 (m, 1 H), 4.3 (dd, 2 H), 4.15 (dd, 2H), 2.3 (m, 6 H), 1.6 (m, 6 H), 1.25 (m, 36 H), 0.9 (t, 3 H).

Dioctanyl monostearin is prepared by melting 200 g (0.56 moles)1-glycerol-rac-monostearin obtained from Spectrum Chemicals (Lot #FC026)in a 1-L reaction flask equipped with a magnetic stirrer, boiling chips,heating mantle, thermometer, and reflux condenser prior to adding 316.7g (1.17 moles) octanoic anhydride (American Tokyo Kasei Inc). Thereaction flask is heated to 250° C. for 10 hours at atmosphericpressure, and the octanoic acid side product is removed by vacuumdistillation at 100 mm Hg, 160° C. The yield of distillate isquantitative. The product is passed through a falling film stillequipped with mesitylne as the boiling solvent (168° C., <1 mm Hg) andthen steam deodorized at 210° C., <1 mm Hg. The yield is 320.2 g (0.52moles, 93.6%) of a brown solid having a capillary melting point of38°-41° C. and a DSC melting point of 37° C. NMR in CDCl₃ (chemicalshifts in ppm) indicate 97.8% product: 5.25 (m, 1 H), 4.3 (dd, 2 H),4.15 (dd, 2 H), 2.3 (m, 6 H), 1.6 (m, 6 H), 1.25 (m, 36 H), 0.9 (t, 9H).

Dicapryl monostearin is prepared by melting 269 g (0.75 moles)1-glycerol-rac-monostearin obtained from Spectrum Chemicals (Lot #FC026)in a 3-L reaction flask equipped with a magnetic stirrer, boiling chips,heating mantle, thermometer, and reflux condenser prior to adding 489.8g (1.5 moles) decanoic (capric) anhydride (TCI Chemicals, lot FC 001).The reaction flask is heated to 200° C. for 10 hours at atmosphericpressure, and the capric acid side product is removed by vacuumdistillation at 100 mm Hg, 160° C. The yield of distillate isquantitative. The brown soft solid product is passed through a fallingfilm still equipped with mesitylne as the boiling solvent (168° C., <1mm Hg) and then steam deodorized at 210° C., <1 mm Hg. The yield is429.98 g (0.64 moles, 85.9%) of a golden yellow soft solid having a DSCmelting point of 35.7° C. and a capillary melting point of 31°-33° C.NMR in CDCl₃ (chemical shifts in ppm) indicates 98% product: 5.25 (m, 1H), 4.3 (dd, 2 H), 4.15 (dd, 2 H), 2.3 (m, 6 H), 1.6 (m, 6 H), 1.25 (m,36 H), 0.9 (t, 9 H).

Dilauryl monostearin is prepared by melting 11.65 g (0.03 moles)1-glycerol-rac-monostearin obtained from Spectrum Chemicals (Lot #FC026)in a 200-mL reaction flask equipped with a magnetic stirrer, boilingchips, heating mantle, thermometer, and reflux condenser prior to adding25 g (0.065 moles) lauric anhydride (TCI Chemicals). The reaction flaskis heated to 200° C. for 10 hours at atmospheric pressure, and thecapric acid side product is removed by vacuum distillation at <5 mm Hg,180° C. The yield of distillate is quantitative. The product is passedthrough a falling film still equipped with mesitylne as the boilingsolvent (168° C., <1 mm Hg) and then steam deodorized at 210° C., <1 mmHg. The yield is 20.1 g (0.58 moles, 4.9%) of a golden yellow solidhaving a DSC melting point of 38.7° C. and a capillary melting point of33°-36° C. NMR in CDCl₃ (chemical shifts in ppm) indicates 98% product:5.25 (m, 1 H), 4.3 (dd, 2 H), 4.15 (dd, 2 H), 2.3 (m, 6 H), 1.6 (m, 6H), 1.25 (m, 36 H), 0.9 (t, 9 H).

The data show a progressive decrease in melting point from 73° C. forthe beta form of tristearin to 38.7° C. for dilauryl monostearin to35°-36° for didecanyl monostearin to 13° C. for dihexanyl monostearin.This result can be correlated with generally expected decreases inmelting points with decreasing sizes of the molecules. However, as thechain length is further decreased, the melting point surprisingly rises:21° for dibutyryl monostearin, 24° C. for dipropionyl monostearin, and38° C. for diacetyl monostearin.

The low melting behavior of the dihexanyl derivative is in agreementwith previously reported data wherein the C₆ triglycerides were found tohave minimum melting points in the C₁₈ C_(n) C₁₈ and C_(n) C_(n) C₁₈series, n=2 to 18 (Jackson, et al., and Jackson and Lutton, citedabove).

Example 39

This example compares and contrasts cocoa butter with various lowcalorie triglycerides in chocolate coating compositions. The DSC meltingprofile of tempered cocoa butter control () which hardens into aslightly waxy form after several months (), is compared with quenchcooled cocoa butter () in FIG. 1.

The coatings are prepared by mixing equal parts confectioner's sugar,cocoa powder, and test fat thoroughly at 55° to 65° C. with 0.5% byweight lecithin. The mixture is then poured into molds and allowed tocool to ambient temperature or refrigerated.

A triglyceride mixture is prepared by the interesterification of 4.5moles triacetin with 1.0 mole hydrogenated canola as outlined in Example20. The resulting mixture was determined by SFC to contain 70% SSL/SLS,27% SLL/LSL, and 3% LLL. A chocolate coating prepared with this fat hada DSC melting profile () and mouthfeel similar to a coating preparedwith cocoa butter () on the first day, but hardened over time asillustrated in FIG. 2 (11 days, ; 17 days, ). The coating had themouthfeel of candlewax after only a few days at room temperature.

Diacetostearin was prepared by the direct esterification of 97% glycerolmonostearate with acetic anhydride as outlined in Example 3. Theresulting mixture was determined by SFC to contain less than 5% SLL/LSLand LLL. A chocolate coating prepared with this fat had a meltingprofile and mouthfeel similar to a coating made with cocoa butter. Thetest coating hardened very slowly over a period of a year to a slightlywaxy form. No bloom was noticeable after 18 months at room temperature,and the flavor did not change compared to a control held in the freezerin a sealed container.

Hydrogenated canola was interesterified with triacetin and tripropioninas described in Example 24 in a ratio of 1:2:2.5. The resulting mixturewas determined by SFC to contain 71% SSL/SLS, 27% SLL/LSL, and 2% LLL.As depicted in FIG. 3, a chocolate coating prepared with this fat had aDSC melting profile () similar to a coating made with cocoa butter ().The test coating stabilized to a slightly higher melting form after twodays ( ), which persisted over the course of the study. The mouth-feelwas acceptable, but the coating was soft. In addition, after 20 days at75° F., a whitish bloom appeared that grew worse as time passed. Thebloom was scraped from the surface, subjected to DSC and SFC analysis,and found to contain mostly SLL/LSL species.

A desirable low calorie triglyceride mixture was prepared byinteresterifying 11 moles triacetin and 1 mole tripropionin withhydrogenated canola as outlined in Example 36. The resulting mixture wasdetermined by SFC to contain 85% SSL/SLS, 14.5% SLL/LSL, and 0.5% LLL.FIG. 4 shows that a coating prepared from this mixture () is slightlysofter, but similar to a coating prepared with cocoa butter (). Thecoating hardens somewhat over time, but didn't become waxy; it has alower DSC melting profile than cocoa butter after a 3-month storage ateither 75° F. or 65° F. No trace of bloom was observed in samples storedat 75° F. after 3 months, and the odor and flavor remained very good.

Example 40

This example compares and contrasts cookies having a shorteningcomponent formulated with low calorie triglycerides of this inventionand control cookies formulated with an all purpose vegetable shortening(Centrasoy™).

Reduced calorie fat mixtures are prepared as described in Examples 24and 36 using interesterification mixtures containing the followingdifferent reactant molar ratios of hydrogenatedcanola:tripropionin:triacetin and analyzed using SFC to determine theSSL/SLS, SLL/LSL, and LLL components as described in Example 21:

    ______________________________________                                        Mixture        SSL/SLS    SLL/LSL   LLL                                       ______________________________________                                        Mixture B from 1:1:11                                                                        82.8       16.1      1.1                                       Mixture C from 1:11:1                                                                        84.8       14.41     0.8                                       Mixture D from 1:3:9                                                                         87.9       11.6      0.5                                       Mixture E from 1:6:6                                                                         84.4       13.8      1.8                                       Mixture F from 1:9:3                                                                         88.0       11.4      0.7                                       ______________________________________                                    

The solid fat index for each mixture is measured using DSC. The areaunder the melting peak curves are integrated to give percent liquid atthe desired temperatures of 0° C., 10° C., 21.1° C., 26.7° C., 33.3° C.,and 37.8° C. These values are then converted to percent solids. Usingthis methodology, the data are obtained are plotted in FIG. 5, with thecontrol depicted as , mixture B as , mixture C as , mixture D as ,mixture E as and mixture F as . It can be seen that at room temperature,mixtures C and F are closest to the control shortening value of about50% solids.

    ______________________________________                                                                 grams                                                ______________________________________                                        To prepare the cookies, mix                                                   fine granulated sugar      72.0                                               brownulated brown sugar    22.5                                               nonfat dry milk            2.3                                                salt                       2.8                                                sodium bicarbonate         2.3                                                and then add                                                                  control or test shortening 90.0.                                              Add high fructose corn syrup                                                                             3.4                                                then ammonium bicarbonate  1.1                                                and vanilla extract         0.34                                              to water                   calculated*                                        and add the water mixture to the shortening mixture.                          Add flour                  calculated*                                        ______________________________________                                    

Sheet and cut the dough according to AACC Method 10-22. Bake at 400° F.for 10 minutes in a National reel test bake oven.

Dough viscosity is measured using a Stevens-LFRA™ texture analyzer.Immediately after preparing the dough, 109 grams are added to the LFRAcup and compressed to a constant volume. A spherical probe is thenplunged into the dough 15 mm at a rate of 2 mm/sec. Five measurementsare taken for each dough and the average load value (grams) is reported.Using this method, cookie dough made using the control shortening had aLFRA value of 112; using mixture B, 1105; using mixture C, 180; usingmixture D, *g flour={(100-13% moisture basis)/ (100-flour moisture%)}*225 g g water=225 g - g flour added+49.5 717; using mixture E, 296;and using mixture F, 136. Desirable processability LFRA values fallbetween about 100 and about 300, so that mixtures C, E, and F areacceptable shortenings in this cookie recipe, but mixtures B and D (highin acetic acid residues) make the dough too stiff.

During baking, the dough blank weights and cookie weights are measuredand recorded. The following equation is then used to calculate thepercent weight loss during baking:

    weight loss=100 * (dbw - cw)/dbw

where dbw=dough blank weight and cw=cookie weight. Final cookie moisturemeasurements are made using a Computrac™ set at 150° C. Three runs ofeach sample are tested and an average moisture in % is recorded. Usingthis methodology, the following data are obtained:

    ______________________________________                                        sample        weight loss                                                                             moisture                                              ______________________________________                                        control       12.32     5.65                                                  B             9.27      7.59                                                  C             8.60      8.56                                                  D             10.51     10.60                                                 E             9.34      7.68                                                  F             6.60      9.62                                                  ______________________________________                                    

All the test compounds have higher moisture, i.e., lower weight lossduring baking, than the control.

After baking, the cookies are measured. Using a micrometer, the cookiediameter/spread (mm) are measured on at least 3 cookies in 4 locations.An average value is obtained and reported as an average cookie diameter.Four cookies are then stacked and the stack height is measured. Averagecookie height is then obtained by dividing by the number of cookies.Using these measurements the following data are obtained:

    ______________________________________                                        sample      diameter (mm)                                                                             height (mm)                                           ______________________________________                                        control     82.65       9.22                                                  B           80.09       15.52                                                 C           70.84       11.76                                                 D           73.40       14.44                                                 E           71.23       13.59                                                 F           71.46       10.17                                                 ______________________________________                                    

All the test shortenings have smaller diameters, but higher stackheights, than the control. Among the materials tested, those with morepropionic acid residues exhibited somewhat less spread and those withless propionic acid residues achieved greater height.

Product color is evaluated using a Minolta Chroma™ meter model CR-210 tomeasure L, a rating of light to dark (<˜30 is dark); a, a sense ofintensity of hue and a measure of red-green; and b, a sense of intensityof chroma and a measure of yellow-blue (roughly comparable to Hunter L,a, and b values). Desirable cookies exhibit red a values and yellow bvalues. Three cookies are measured three times and averaged for both topand bottom colors. Using this technique, the following data areobtained:

    ______________________________________                                        sample     TOP: L,a,b  BOTTOM: L,a,b                                          ______________________________________                                        control    65.09,6.11,33.17                                                                          45.46,14.93,29.44                                      B          63.45,7.03,31.49                                                                          42.78,16.63,30.70                                      C          62.44,6.75,30.68                                                                          45.41,15.11,31.71                                      D          63.60,6.10,30.30                                                                          43.10,15.98,31.11                                      E          56.80,9.29,30.11                                                                          39.76,15.98,28.94                                      F          61.78,6.54,31.08                                                                          45.66,15.82,30.96                                      ______________________________________                                    

With the exception of sample E, which produced a darker cookie, thereare no significant differences in any of the color values.

Texture of the baked cookies is evaluated using an Instron™ 4501Universal Testing machine, which punctures the cookies and measuresresistance to a small probe. Values for stress and moduli, which can becorrelated with hardness, fracturability and/or brittleness, arecalculated based on the resistant force versus distance. Using thistechnique, the following data are obtained:

    ______________________________________                                        sample     stress (kg/mm.sup.2)                                                                      moduli (kg/mm.sup.2)                                   ______________________________________                                        control    0.435       8.07                                                   B          0.638       17.17                                                  C          0.293       9.20                                                   D          0.115       3.15                                                   E          0.168       6.31                                                   F          0.154       4.69                                                   ______________________________________                                    

The varying degrees of stress and moduli obtained suggest that texturalattributes from cake-like to a dense snap cookie can be achieved.

Example 41

Like Example 40 above, this example evaluates cookies having ashortening component formulated with low calorie triglycerides of thisinvention, except that the triglycerides are blends rather thaninteresterified mixtures.

Low calorie chocolate chips are first prepared. Diacetyl stearin, 150 g,is melted and blended with 150 g cocoa powder, 150 g confectioner'ssugar and 4.5 g lecithin, deposited into nibs and processed into chips.

A blend of 35% diacetyl stearin and 65% dipropionyl stearin, which had abroad DSC melting range between about -15° and 40° C., is employed inthe cookie recipe of Example 40 and compared with an all purposevegetable shortening control cookie. Before baking, 112.5 gramschocolate chips formulated as described above are mixed into the testdough; Wilbur's real chocolate chips are used in the control. Thecookies are baked at 420° for 10 minutes.

The baking behavior is depicted in FIG. 6, which compares the controlcookie with the low calorie dipropionyl stearin/diacetyl stearinshortening cookie. At the two minute mark, the low calorie dough blankstarted to spread in an unusual steplike pattern. The cookies achieved afairly high rise at 3 minutes and did not start to spread out untilalmost 4 minutes into the bake. Collapse occurred around the 5 minutemark and setting and browning began to occur at 6 minutes. The finalcookie had a nice brown color with low spread and high stack height.Color analysis using the Minolta Chroma™ meter described in the previousExample gave an L value of 59.56, an a value of 8.04 and a b value of34.1. The diacetyl stearin chocolate chips stood up well under baking.

The experiment is repeated comparing control cookies with cookies havingshortening components comprising diacetyl stearin and either dibutyrlstearin or dipropionyl stearin. FIG. 7 shows DSC solid fat indices ofdifferent blends of diacetyl stearin with dipropionyl or dibutyrylstearin compared with a vegetable oil shortening control (). In thefigure, is a 1:1, is a 1:2 and is a 2:1 blend of diacetyl stearin anddibutyryl stearin; is a 1:1, , a 1:2, and , a 4:1 blend of diacetylstearin and dipropionyl stearin.

Using the same control cookies containing an all purpose vegetableshortening and real Wilbur's chocolate chips, cookies formulated with ashortening comprising diacetyl stearin and dibutyryl stearin blended inequal proportions and diacetyl stearin chocolate chips (recipe G), andcookies formulated with a shortening comprising diacetyl stearin anddipropionyl stearin blended in equal proportions and diacetyl stearinchocolate chips (recipe H) are prepared and baked.

Geometric and color measurements using the methodology of the aboveExample yielded the following data:

    ______________________________________                                        recipe stack height (mm)                                                                          width (mm)  color (L.a,b)                                 ______________________________________                                        control                                                                              1.125        8.1         56.51,6.99,27.81                              G      1.250        7.0         51.97,10.84,29.82                             H      1.125        7.5         57.43,8.23,30.24                              ______________________________________                                    

The control cookies came out flat and pale. The recipe G cookiesrequired 11 minutes to bake (instead of 10) and came out dark andmottled, with high stack height and little spread. The recipe H cookieshad good stack height, good spread and good color.

Example 42

    ______________________________________                                        Cookies. Another cookie batch is prepared by mixing                           Ingredient           grams                                                    ______________________________________                                        Granulated Sugar     12.8                                                     Brownulated Brown Sugar                                                                            4.0                                                      Nonfat Dry Milk      0.4                                                      Salt                 0.5                                                      Sodium Bicarbonate   0.4                                                      A Dibutylstearin (35%) and                                                                         16.0                                                     Corn oil (65%) Blend                                                          To this is added                                                              Water                8.8                                                      High Fructose Corn Syrup                                                                           0.6                                                      Ammonium Bicarbonate 0.2                                                      Then Flour           40.0                                                     ______________________________________                                    

The dough is sheeted, cut and baked in the usual manner.

Example 43

    ______________________________________                                        Ice Cream. Chocolate ice cream is prepared by mixing                          Ingredient             parts                                                  ______________________________________                                        Water                  60.6                                                   Example 37 Triglyceride Mixture B                                                                    10.0                                                   Nonfat Dry Milk        10.0                                                   Sugar                  10.0                                                   Corn Syrup             6.0                                                    Dricol ™ Texture Enhancer                                                                         0.3                                                    Cocoa Light            3.0                                                    Lecithin               0.1                                                    ______________________________________                                    

The ingredients are heated to pasturize, then cooled slightly,homogenized, and pumped into a heat exhanger whereupon the temperatureis rapidly reduced. After the initiation of fat crystallization, themixture is frozen.

Example 44

    ______________________________________                                        Cream Filling. To make a cream filling, combine                               Ingredient            grams                                                   ______________________________________                                        Sugar (6×)      376                                                     with Example 2 Diacetyl Stearin                                                                     160                                                     Example 14 Dipropionyl Stearin                                                                      24                                                      Example 36 Dihexanyl Stearin                                                                        14                                                      Lecithin              2                                                       and Vanilla           0.3                                                     ______________________________________                                    

The filling had a smooth texture and mouthfeel and a solids content of90% at 50° F., 78% at 70° F., 60% at 80° F., 15% at 92° F., and 0% at100° F., which remained stable a week at room temperature.

Example 45

    ______________________________________                                        Sandwich Cookies. Basecakes may be prepared by combining                                             parts                                                  ______________________________________                                        Flour                    48.0                                                 High Fructose Corn Syrup 12.0                                                 Sugar (6X)               10.0                                                 Example 24 1:2.5:2.5 Triglyceride Mixture                                                              10.0                                                 Dutched Cocoa            5.0                                                  Corn Syrup (42 D.E.)     3.0                                                  Dextrose                 2.0                                                  Frozen Whole Eggs        2.0                                                  Salt                     0.3                                                  Sodium Bicarbonate       0.2                                                  Lecithin                 0.2                                                  Vanilla                  0.2                                                  Ammonium Bicarbonate     0.1                                                  Water                    7.0                                                  ______________________________________                                    

mixing well, rotary molding, baking and cooling. Sandwich cookies areprepared by filling the basecakes with the filler of previous Example 44in a weight ratio of 100 parts basecake to 40.5 parts filler.

The cookies may, optionally, be enrobed with a coating prepared byblending 150 g melted diacetyl stearin, 150 g dutched cocoa powder, 150g confectioner's sugar and 4.5 g lecithin.

Example 46

Shortening. A shortening may be prepared by interesterifying 2 moles oftributyrin with 1 mole of hydrogenated canola as outlined in Example 20.

Example 47

Margarine. A stick margarine may be prepared by emulsifying

    ______________________________________                                                            parts                                                     ______________________________________                                        Oil Phase Ingredients                                                         Example 20 1:2.5                                                              Triglyceride Mixture  40                                                      Liquid corn oil       40                                                      Lecithin              0.3                                                     Mono- and Di-glycerides                                                                             0.21                                                    Margarine Flavor and Color                                                                          0.0062                                                  with Aqueous Phase Ingredients                                                Water                 16.4                                                    Whey                  1.00                                                    Salt                  2.00                                                    Sodium Benzoate       0.086                                                   ______________________________________                                    

and passing the emulsion through a cooled, scraped-surface heatexchanger in the usual process.

Example 48

Low Fat Spread. A 60% table spread may be prepared by emulsifying

    ______________________________________                                                            parts                                                     ______________________________________                                        Oil Phase Ingredients                                                         A 65:35 Blend of Corn Oil:                                                    Example 20 1:1.25 Triglycerides                                                                     59.58                                                   Lecithin              0.20                                                    Distilled Monoglycerides from                                                 Unhydrogenated Sunflower Oil                                                                        0.20                                                    Beta-carotene and Vitamin                                                     A Palmitate in Corn Oil                                                                             0.005                                                   Flavor                0.010                                                   with Aqueous Phase Ingredients                                                Water                 37.86                                                   Salt                  2.00                                                    Potassium Sorbate     0.10                                                    Phosphoric Acid       0.04                                                    ______________________________________                                    

and passing the emulsion through a cooled, scraped-surface heatexchanger in the usual process.

Example 49

Low Fat Spread. A 40% table spread may be prepared by emulsifying

    ______________________________________                                                            parts                                                     ______________________________________                                        Oil Phase Ingredients                                                         A 75:25 Blend of Corn Oil:                                                    Example 14 Triglycerides                                                                            39.38                                                   Lecithin              0.10                                                    Distilled Monoglycerides from                                                                       0.50                                                    Unhydrogenated Sunflower Oil                                                  Flavor                0.010                                                   with Aqueous Phase Ingredients                                                Water                 57.86                                                   Salt                  2.00                                                    Potassium Sorbate     0.10                                                    Calcium Disodium EDTA 0.006                                                   ______________________________________                                    

and passing the emulsion through a cooled, scraped-surface heatexchanger in the usual process.

Example 50

Spray Oil. A spray oil may be prepared by interesterifying 12 molestributyrin with 1 mole of hydrogenated canola as outlined in Example 20.

Example 51

Low calorie triglycerides of this invention bearing two short residuesand one long, saturated moiety include the following example compounds:

1-acetyl-3-palmitoyl-2-propionyl glyceride2-acetyl-1-palmitoyl-3-propionyl glyceride2-acetyl-1-propionyl-3-stearoyl glyceride1-acetyl-2-propionyl-3-stearoyl glyceride1-acetyl-3-arachidoyl-2-propionyl glyceride2-acetyl-1-arachidoyl-3-propionyl glyceride1-acetyl-3-behenoyl-2-propionyl glyceride2-acetyl-1-behenoyl-3-propionyl glyceride 1-acetyl-2-butyryl-3-palmitoylglyceride 2-acetyl-1-butyryl-3-palmitoyl glyceride2-acetyl-1-butyryl-3-stearoyl glyceride 1-acetyl-2-butyryl-3-stearoylglyceride 1-acetyl-3-arachidoyl-2-butyryl glyceride2-acetyl-1-arachidoyl-3-butyryl glyceride 1-acetyl-3-behenoyl-2-butyrylglyceride 2-acetyl-1-behenoyl-3-butyryl glyceride1-acetyl-3-palmitoyl-2-valeryl glyceride 2-acetyl-1-palmitoyl-3-valerylglyceride 2-acetyl-1-stearoyl-3-valeryl glyceride1-acetyl-3-stearoyl-2-valeryl glyceride 1-acetyl-3-arachidoyl-2-valerylglyceride 2-acetyl-1-arachidoyl-3-valeryl glyceride1-acetyl-3-behenoyl-2-valeryl glyceride 2-acetyl-1-behenoyl-3-valerylglyceride 1-butyryl-3-palmitoyl-2-propionyl glyceride2-butyryl-1-palmitoyl-3-propionyl glyceride2-butyryl-1-propionyl-3-stearoyl glyceride1-butyryl-3-stearoyl-2-propionyl glyceride1-arachidoyl-2-butyryl-3-propionyl glyceride 101-arachidoyl-3-butyryl-2-propionyl glyceride1-behenoyl-3-butyryl-2-propionyl glyceride1-behenoyl-2-butyryl-3-propionyl glyceride1-palmitoyl-2-propionyl-3-valeryl glyceride1-palmitoyl-3-propionyl-2-valeryl glyceride2-propionyl-1-stearoyl-3-valeryl glyceride1-propionyl-3-stearoyl-2-valeryl glyceride1-arachidoyl-2-propionyl-3-valeryl glyceride1-arachidoyl-3-propionyl-2-valeryl glyceride1-behenoyl-2-propionyl-3-valeryl glyceride1-behenoyl-3-propionyl-2-valeryl glyceride1-acetyl-2-palmitoyl-3-propionyl glyceride1-acetyl-3-propionyl-2-stearoyl glyceride1-acetyl-2-arachidoyl-3-propionyl glyceride1-acetyl-2-behenoyl-3-propionyl glyceride 1-acetyl-3-butyryl-2-palmitoyl glyceride 1-acetyl-3-butyryl-2-stearoyl glyceride1-acetyl-2-arachidoyl-3-butyryl glyceride 1-acetyl-2-behenoyl-3-butyrylglyceride 1-acetyl-2-palmitoyl-3-valeryl glyceride1-acetyl-2-stearoyl-3-valeryl glyceride 1-acetyl-2-arachidoyl-3-valerylglyceride 1-acetyl-2-behenoyl-3-valeryl glyceride1-butyryl-2-palmitoyl-3-propionyl glyceride1-butyryl-2-stearoyl-3-propionyl glyceride2-arachidoyl-1-butyryl-3-propionyl glyceride2-behenoyl-1-butyryl-3-propionyl glyceride2-palmitoyl-1-propionyl-3-valeryl glyceride1-propionyl-2-stearoyl-3-valeryl glyceride2-arachidoyl-1-propionyl-3-valeryl glyceride2-behenoyl-1-propionyl-3-valeryl glyceride

Low calorie triglyceride mixtures of this invention can also include thefollowing example compounds:

SSL Derivatives

1,2-diacetyl-3-palmitoyl glyceride 1,2-diacetyl-3-stearoyl glyceride1,2-diacetyl-3-arachidoyl glyceride 1,2-diacetyl-3-behenoyl glyceride1-palmitoyl-2,3-dipropionyl glyceride 1,2-dipropionyl-3-stearoylglyceride 1-arachidoyl-2,3-dipropionyl glyceride1-behenoyl-2,3-dipropionyl glyceride 1,2-dibutyryl-3-palmitoyl glyceride1,2-dibutyryl-3-stearoyl glyceride 1-arachidoyl-2,3-dibutyryl glyceride1-behenoyl-2,3-dibutyryl glyceride

SLS Derivatives

1,3-diacetyl-2-palmitoyl glyceride 1,3-diacetyl-2-stearoyl glyceride1,3-diacetyl-2-arachidoyl glyceride 1,3-diacetyl-2-behenoyl glyceride2-palmitoyl-1,3-dipropionyl glyceride 1,3-dipropionyl-2-stearoylglyceride 2-arachidoyl-1,3-dipropionyl glyceride2-behenoyl-1,3-dipropionyl glyceride 1,3-dibutyryl-2-palmitoyl glyceride1,3-dibutyryl-2-stearoyl glyceride -arachidoyl-1,3-dibutyryl glyceride-behenoyl-1,3-dibutyryl glyceride

LLS Derivatives

1-acetyl-2,3-dipalmitoyl glyceride 1-acety1-2,3-distearoyl glyceride1-acetyl-2,3-diarachidoyl glyceride 1-acetyl-2,3-dilignoceroyl glyceride1-acetyl-2,3-dibehenoyl glyceride 1,2-dipalmitoyl-3-propionyl glyceride1-propionyl-2,3-distearoyl glyceride 1,2-diarachidoyl-3-propionylglyceride 2-propionyl-1,3-distearoyl glyceride1,2-dibehenoyl-3-propionyl glyceride 1,2-diarachidoyl-3-butyrylglyceride 1-butyryl-2,3-dipalmitoyl glyceride 1-butyryl-2,3-dicerotoylglyceride 1-acetyl-2-palmitoyl-3-stearoyl glyceride1-acetyl-3-palmitoyl-2-stearoyl glyceride1-acetyl-3-arachidoyl-2-palmitoyl glyceride1-acetyl-2-arachidoyl-3-palmitoyl glyceride1-acetyl-3-behenoyl-2-palmitoyl glyceride1-acetyl-2-behenoyl-3-palmitoyl glyceride1-acetyl-2-arachidoyl-3-stearoyl glyceride1-acetyl-3-behenoyl-2-stearoyl glyceride1-acetyl-3-arachidoyl-2-stearoyl glyceride1-acetyl-2-behenoyl-3-stearoyl glyceride1-acetyl-2-arachidoyl-3-behenoyl glyceride1-acetyl-3-arachidogyl-2-behenoyl glyceride1-palmitoyl-3-propionyl-2-stearoyl glyceride2-palmitoyl-1-propionyl-3-stearoyl glyceride1-arachidoyl-2-palmitoyl-3-propionyl glyceride1-behenoyl-2-palmitoyl-3-propionyl glyceride2-arachidoyl-1-palmitoyl-3-propionyl glyceride2-behenoyl-1-palmitoyl-3-propionyl glyceride1-arachidoyl-3-propionyl-2-stearoyl glyceride1-behenoyl-3-propionyl-2-stearoyl glyceride2-arachidoyl-1-propionyl-3-stearoyl glyceride2-behenoyl-1-propionyl-3-stearoyl glyceride1-butyryl-2-palmitoyl-3-stearoyl glyceride2-arachidoyl-1-butyryl-3-palmitoyl glyceride1-butyryl-3-palmitoyl-2-stearoyl glyceride1-arachidoyl-3-butyryl-2-palmitoyl glyceride2-behenoyl-1-butyryl-3-palmitoyl glyceride1-behenoyl-3-butyryl-2-palmitoyl glyceride1-arachidoyl-3-butyryl-2-stearoyl glyceride2-arachidoyl-1-butyryl-3-stearoyl glyceride2-behenoyl-1-butyryl-3-stearoyl glyceride1-behenoyl-3-butyryl-2-stearoyl glyceride1-arachidoyl-2-behenoyl-3-butyryl glyceride2-arachidoyl-1-behenoyl-3-butyryl glyceride

LSL Derivatives

2-acetyl-1,3-dipalmitoyl glyceride 2-acetyl-1,3-distearoyl glyceride2-acetyl-1,3-diarachidoyl glyceride 2-acetyl-1,3-dibehenoyl glyceride1,3-diarachidoyl-2-propionyl glyceride 1,3-dibehenoyl-2-propionylglyceride 2-butyryl-1,3-dipalmitoyl glyceride1,3-dipalmitoyl-2-propionyl glyceride 1,3-diarachidoyl-2-butyrylglyceride 1,3-dibehenoyl-2-butyryl glyceride2-acetyl-1-palmitoyl-3-stearoyl glyceride2-acetyl-1-behenoyl-3-palmitoyl glyceride2-acetyl-1-arachidoyl-3-palmitoyl glyceride2-acetyl-1-arachidoyl-3-stearoyl glyceride2-acetyl-1-behenoyl-3-stearoyl glyceride1-palmitoyl-2-propionyl-3-stearoyl glyceride1-arachidoyl-3-palmitoyl-2-propionyl glyceride1-behenoyl-3-palmitoyl-2-propionyl glyceride1-behenoyl-2-propionyl-3-stearoyl glyceride1-arachidoyl-3-behenoyl-2-propionyl glyceride2-butyryl-1-palmitoyl-3-stearoyl glyceride

1-arachidoyl-2-butyryl-3-palmitoyl glyceride

1-behenoyl-2-butyryl-3-palmitoyl glyceride1-arachidoyl-2-butyryl-3-stearoyl glyceride

1-behenoyl-2-butyryl-3-stearoyl glyceride

1-arachidogyl-3-behenoyl-2-butyryl glyceride

The above description is for the purpose of teaching the person ofordinary skill in the art how to practice the present invention, and itis not intended to detail all those obvious modifications and variationsof it which will become apparent to the skilled worker upon reading thedescription. It is intended, however, that all such obviousmodifications and variations be included within the scope of the presentinvention, which is defined by the following claims.

What is claimed is:
 1. A chocolate confectionery composition comprisinga chocolate flavor, a sweetener, and a fat component comprising at leastabout 10 weight % triglycerides of the formulae ##STR23## wherein eachR, independently, is a long chain saturated fatty acid residue havingbetween 16 and 22 carbons; andeach R' is a butyric acid residue whereinsaid fat component exhibits a melting profile similar to cocoa butter.2. A composition according to claim 1 wherein at least about 70% of theR groups are stearic acid residues.
 3. A composition according to claim2 wherein at least about 90% of the R residues are stearic acidresidues.
 4. A composition according to claim 1 wherein the fatcomponent comprises at least about 15 mole % of said triglycerides.
 5. Acomposition according to claim 4 wherein the fat component comprises atleast about 20 mole % of said triglycerides.
 6. A composition accordingto claim 4 wherein the fat component comprises at least about 25 mole %of said triglycerides.
 7. A composition according to claim 6 wherein thefat component comprises at least about 30 mole % of said triglycerides.8. A composition according to claim 7 wherein the fat componentcomprises at least about 40 mole % of said triglycerides.
 9. Acomposition according to clam 1 wherein the R groups are derived fromoils selected from the group consisting of soybean oil, canola, andcottonseed oil.
 10. A chocolate bar comprising the composition ofclaim
 1. 11. A chocolate composition containing a sweetener, a chocolateflavor, and a fat component, the fat component comprising at least 25weight % of a mixture of at least two triglycerides of the followingformulae ##STR24## wherein each R, independently, is a long chainsaturated fatty acid residues having between 16 and 22 carbons; andeachR', independently is a short chain acid residue derived from acidsselected from the group consisting of butyric acid, mixtures of aceticand propionic acid, mixtures of propionic and butyric acid, mixtures ofacetic, propionic, and butyric acid and mixtures of acetic and butyricacid, and the mixture contains greater than about 25% LLS and LSLspecies and the fat component exhibits a melting profile similar tococoa butter.
 12. A composition according to claim 11 wherein at leastabout 70% of the R groups are derived from stearic acid residues.
 13. Acomposition according to claim 11 wherein the R groups are derived fromoils selected from the group consisting of soybean oil, canola, andcottonseed oil.
 14. A composition according to claim 11 wherein themixture contains up to about 40% LLS and LSL species.
 15. A compositionaccording to claim 11 wherein the R' groups are derived from short acidsselected from the group consisting of a mixture of acetic and propionieacid and a mixture of acetic and butylie acid.
 16. An edible coatingcomposition comprising a fat ingredient containing at least 25% of twoor more low calorie triglycerides of the formula ##STR25## wherein the Rgroups are, independently, long chain saturated fatty acid residueshaving between 16 and 22 carbons; andthe R' groups are, independently,derived from propionic acid, butyric acid, or a mixture of these witheach other or with acetic acid wherein said fat ingredient has a meltingpoint of about 32° to about 38° C., a solids content of at least about50% at about 10° C., and a solids content of less than about 5% at about30° C.
 17. A composition according to claim 16 wherein the LLS and LSLspecies comprise less than 15 mole % of the low calorie triglycerides.18. A composition according to claim 16 wherein the LLS and LSL speciescomprise between about 25 to 40 mole % of the low calorie triglycerides.19. A composition according to claim 16 wherein the R groups are derivedfrom oils seleeted from the group consisting of soybean oil, canola, andcottonseed oil.
 20. A food product selected from the group consisting ofbaked products, snack food products and nuts coated with the coatingcomposition according to claim
 16. 21. A composition according to claim16 wherein the R' groups comprise a mixture of acetic acid and butyricacid residues.
 22. A composition according to claim 16 wherein the R'groups comprise a mixture of acetic, propionic, and butyric acidresidues.